Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent

ABSTRACT

A method of nucleating a propylene homo- or copolymer, the method comprising contacting the propylene polymer with a semi-crystalline branched or coupled polymeric nucleating agent under nucleation conditions. In one embodiment, the propylene homopolymer is characterized as having  13 C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the peaks of about equal intensity. In another embodiment, the copolymer is characterized as comprising at least about 60 weight percent (wt %) of units derived from propylene, and as having at least one of the following properties: (i)  13 C NMR peaks corresponding to a regio-error at about 14.6 and about 15.7 ppm, the peaks of about equal intensity, (ii) a B-value greater than about 1.4 when the comonomer content, i.e., the units derived from ethylene and/or the unsaturated comonomer(s), of the copolymer is at least about 3 wt %, (iii) a skewness index, S ix , greater than about −1.20, (iv) a DSC curve with a T me  that remains essentially the same and a T max  that decreases as the amount of comonomer, i.e., the units derived from ethylene and/or the unsaturated comonomer(s), in the copolymer is increased, and (v) an X-ray diffraction pattern that reports more gamma-form crystals than a comparable copolymer prepared with a Ziegler-Natta (Z-N) catalyst.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.10/914,800, filed Aug. 10, 2004, and now U.S. Pat. No. 7,060,754, whichis a division of U.S. patent application Ser. No. 10/289,145, filed Nov.5, 2002, and now U.S. Pat. No. 6,927,256, which also claims the benefitunder 35 USC §119(e) of U.S. Provisional Application Nos. 60/338,881 and60/378,204 filed Nov. 6, 2001 and May 5, 2002, respectively.

FIELD OF THE INVENTION

This invention relates to crystallizing polymers. In one aspect, theinvention relates to crystallizing polypropylene while in anotheraspect, the invention relates to crystallizing polypropylene with theaid of a nucleating agent. In another aspect, the invention relates tocrystallizing polypropylene with the aid of a branched or coupledpolypropylene nucleating agent.

BACKGROUND OF THE INVENTION

Polypropylene in its many and varied forms is a long establish staple ofthe polymer industry. Depending upon its form, it exhibits a number ofdesirable properties including toughness (as measured by any of a numberof impact tests, e.g., notched Izod, dart drop, etc.), stiffness (asmeasured by any of a number of modulus tests e.g., Young's), clarity,chemical resistance and heat resistance. Often a particular combinationof properties is desired that requires a balancing of various propertiesagainst one another (e.g., stiffness against toughness).

Crystalline polypropylene, typically a homopolymer, is used extensivelyin various moldings because it exhibits desirable mechanical (e.g.,rigidity) and chemical resistance properties. For applications thatrequire impact resistance (e.g., automobile parts, appliance facia,packaging, etc.), a copolymer of propylene and ethylene (P/E copolymer)and/or one or more α-olefins is used, or a blend of crystallinepolypropylene with one or more polymers that exhibit good impactresistance, e.g., ethylene-propylene (EP) and/orethylene-propylene-diene (EPDM) rubber. For applications that requiretoughness and/or heat resistance (e.g., films), preferably thepolypropylene has a relatively low melt flow rate (MFR) or expressedalternatively, a relatively high weight average molecular weight(M_(w)). For applications that require good processing characteristics(e.g., fibers), preferably the polypropylene has a relatively narrowpolydisperity or molecular weight distribution (MWD), e.g., less than3.5.

One method of modifying the properties of polypropylene, either as ahomopolymer or as a copolymer, is to modify its crystalline structure.The onset of crystallinity is known as nucleation, and this may occurrandomly throughout the polymer matrix as the individual polymermolecules begin to align. Alternatively, nucleation may occur at theinterface of a foreign impurity or an intentionally added nucleatingagent. The proper use of nucleating agents can result not only in uniqueand desirable crystalline structures, but they can also promote theefficiency of a given process by shortening process times, initiatingnucleation at higher temperatures and the like.

SUMMARY OF THE INVENTION

In a first embodiment, the invention is a method of nucleating apropylene homopolymer or a propylene copolymer comprising propylene andat least one of ethylene and an unsaturated comonomer, e.g., a C₄₋₂₀α-olefin, C₄₋₂₀ diene, styrenic compound, etc., the method comprisingcontacting the propylene homopolymer or copolymer with asemi-crystalline branched or coupled polymeric nucleating agent.

In a second embodiment, the invention is a method of nucleating apropylene homopolymer characterized as having ¹³C NMR peakscorresponding to a regio-error at about 14.6 and about 15.7 ppm, thepeaks of about equal intensity, the method comprising contacting thepropylene homopolymer with a semi-crystalline branched or coupledpolymeric nucleating agent. Preferably, the propylene homopolymer ischaracterized as having substantially isotactic propylene sequences,i.e., the sequences have an isotactic triad (mm) measured by ¹³C NMR ofgreater than about 0.85. These propylene homopolymers typically have atleast 50 percent more of this regio-error than a comparablepolypropylene homopolymer prepared with a Ziegler-Natta catalyst. A“comparable” polypropylene as here used means an isotactic propylenehomopolymer having the same weight average molecular weight, i.e.,within plus or minus 10 wt %.

In a third embodiment, the invention is a method of nucleating apropylene copolymer comprising at least about 60 weight percent (wt %)of units derived from propylene, about 0.1-35 wt % of units derived fromethylene, and 0 to about 35 wt % of units derived from one or moreunsaturated comonomers, with the proviso that the combined weightpercent of units derived from ethylene and the unsaturated comonomerdoes not exceed about 40, the method comprising contacting the propylenecopolymer with a semi-crystalline branched or coupled polymericnucleating agent. These copolymers are also characterized as having atleast one of the following properties: (i) ¹³C NMR peaks correspondingto a regio-error at about 14.6 and about 15.7 ppm, the peaks of aboutequal intensity, (ii) a B-value greater than about 1.4 when thecomonomer content, i.e., the units derived from ethylene and/or theunsaturated comonomer(s), of the copolymer is at least about 3 wt %,(iii) a skewness index, S_(ix), greater than about −1.20, (iv) a DSCcurve with a T_(me) that remains essentially the same and a T_(max) thatdecreases as the amount of comonomer, i.e., the units derived fromethylene and/or the unsaturated comonomer(s), in the copolymer isincreased, and (v) an X-ray diffraction pattern that reports moregamma-form crystals than a comparable copolymer prepared with aZiegler-Natta (Z-N) catalyst. Typically the polymers of this embodimentare characterized by at least two of these properties. Certain of thepolymers of this embodiment are characterized by at least three of theseproperties, while other polymers of this embodiment are characterized byat least four or even all five of these properties.

With respect to the X-ray property of subparagraph (v) above, a“comparable” copolymer is one having the same monomer composition within10 wt %, and the same Mw within 10 wt %. For example, if an inventivepropylene/ethylene/1-hexene copolymer is 9 wt % ethylene and 1 wt %1-hexene and has a Mw of 250,000, then a comparable polymer would havefrom 8.1-9.9 wt % ethylene, 0.9-1.1 wt % 1-hexene, and a Mw between225,000 and 275,000, prepared with a Ziegler-Natta catalyst.

In a fourth embodiment, the invention is a method of nucleating apropylene copolymer comprising at least about 60 wt % of the unitsderived from propylene, and between about 0.1 and 40 wt % the unitsderived from the unsaturated comonomer, the method comprising contactingthe propylene copolymer with a semi-crystalline branched or coupledpolymeric nucleating agent. These copolymers are also characterized ashaving at least one of the following properties: (i) ¹³C NMR peakscorresponding to a regio-error at about 14.6 and about 15.7 ppm, thepeaks of about equal intensity, (ii) a B-value greater than about 1.4when the comonomer content, i.e., the units derived from the unsaturatedcomonomer(s), of the copolymer is at least about 3 wt %, (iii) askewness index, S_(ix), greater than about −1.20, (iv) a DSC curve witha T_(me) that remains essentially the same and a T_(max) that decreasesas the amount of comonomer, i.e., the units derived from the unsaturatedcomonomer(s), in the copolymer is increased, and (v) an X-raydiffraction pattern that reports more gamma-form crystals than acomparable copolymer prepared with a Ziegler-Natta (Z-N) catalyst.Typically the polymers of this embodiment are characterized by at leasttwo of these properties. Certain of the polymers of this embodiment arecharacterized by at least three of these properties, while otherpolymers of this embodiment are characterized by at least four or evenall five of these properties.

The propylene/ethylene and propylene/unsaturated comomoner copolymersdescribed in the third and forth embodiments of this invention areoccasionally referred to, individually and collectively, as “P/E*copolymers” or a similar term. P/E* copolymers are a unique subset ofP/E copolymers. For purposes of this disclosure, P/E copolymers comprise50 weight percent or more propylene while EP (ethylene-propylene)copolymers comprise 51 weight percent or more ethylene. As here used,“comprise . . . propylene”, “comprise . . . ethylene” and similar termsmean that the polymer comprises units derived from propylene, ethyleneor the like as opposed to the compounds themselves.

In other embodiments, the invention is the P/E* copolymer in combinationwith the semi-crystalline coupled or branched polymeric nucleating agentbefore, during and/or after the on the onset of crystallization, thecrystallized polypropylene in combination with one or more otherpolymers, and the crystallized polypropylene as a fabricated article,e.g., film, sheet, foam, fiber, pouches, injection molded, extrudedcalendered and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the unusual comonomer distribution of apropylene/ethylene (P/E*) copolymer made with a metal-centered,heteroaryl ligand catalyst.

FIGS. 2A and 2B show a comparison of the DSC heating traces of thepropylene/ethylene (P/E) copolymer of Comparative Example 1 and the P/E*copolymer of Example 2, respectively.

FIG. 3 shows a comparison of the Tg data of a P/E* copolymer and aconventional Ziegler-Natta (Z-N) catalyzed P/E copolymer at equivalentcrystallinity.

FIG. 4 shows a comparison of the Tg data of a P/E* copolymer and aconventional constrained geometry catalyst (CGC) P/E copolymer at thesame ethylene content.

FIG. 5 shows a comparison of a TREF curve for a conventional metallocenecatalyzed P/E copolymer and a P/E* copolymer.

FIG. 6 shows the ¹³C NMR spectrum of the propylene homopolymer productof Example 7, prepared using Catalyst G. This spectrum shows the highdegree of isotacticity of the product.

FIG. 7 shows the ¹³C NMR Spectrum of the propylene homopolymer productof Example 8, prepared using Catalyst H. This spectrum is shown at anexpanded Y-axis scale relative to FIG. 6 in order to more clearly showthe regio-error peaks.

FIG. 8 shows the ¹³C NMR Spectrum of the P/E* copolymer product ofExample 2 prepared using Catalyst G.

FIG. 9 shows the ¹³C NMR Spectrum of the P/E copolymer product ofComparative Example 1 prepared using metallocene Catalyst Edemonstrating the absence of regio-error peaks in the region around 15ppm.

FIGS. 10A-10J show the chemical structures of various catalysts.

FIGS. 11A and 11B show the DSC heating and cooling traces of thepropylene homopolymer of Example 8, prepared using Catalyst H.

FIG. 12 shows a comparison of the skewness index for a P/E* copolymerand that of several conventional P/E copolymers.

FIG. 13 compares the melting endotherms of Samples 8 and 22a of Example11.

FIG. 14 demonstrates the shift in peak melting temperature towards lowertemperature for samples of certain P/E*copolymers of Example 11.

FIG. 15 is a plot of the temperature at which approximately 1 percentcrystallinity remains in DSC samples of Example 11.

FIG. 16 shows the variance relative to the first moment of the meltingendotherm as a function of the heat of melting of various samples ofExample 11.

FIG. 17 shows the maximum heat flow normalized by the heat of melting asa function of the heat of melting for various samples of Example 11.

FIG. 18 illustrates that the rate at which the last portion ofcrystallinity disappears in the P/E* polymers is significantly lowerthan for metallocene polymers.

FIGS. 19A and 19B report the increase in Tc onset and peak ofcrystallization temperature after the addition of various nucleatingagents to two P/E* copolymers.

FIG. 20 reports the difference of (Tc, blend)−(Tc, base) for six P/E*and two P/E copolymers blended with a high crystalline propropylenehomopolymer resin.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Molecular Weight

The weight average molecular weight (Mw) of the crystallizable propylenepolymers used in the practice of this invention can vary widely, buttypically it is between about 30,000 and 1,000,000 (with theunderstanding that the only limit on the minimum or the maximum M_(w) isthat set by practical considerations). “Low molecular weight”, “lowweight average molecular weight”, “low Mw” and similar terms mean aweight average molecular weight of less than about 200,000, morepreferably less than about 175,000 and even more preferably less thanabout 150,000. “High molecular weight”, “high weight average molecularweight”, “high Mw” and similar terms mean a weight average molecularweight of at least about 250,000, preferably of at least about 300,000and more preferably 350,000, and more preferably at least about 400,000.

Polydispersity

The polydispersity of the crystallizable propylene polymers used in thepractice of this invention is typically between about 2 and about 6.“Narrow polydisperity”, “narrow molecular weight distribution”, “narrowMWD” and similar terms mean a ratio (M_(w)/M_(n)) of weight averagemolecular weight (M_(w)) to number average molecular weight (M_(n)) ofless than about 3.5, preferably less than about 3.0, more preferablyless than about 2.8, more preferably less than about 2.5, and mostpreferably less than about 2.3. Polymers for use in fiber and extrusioncoating applications typically have a narrow polydispersity.

Gel Permeation Chromatography

Molecular weight distribution of the crystallizable propylene polymersis determined using gel permeation chromatography (GPC) on a PolymerLaboratories PL-GPC-220 high temperature chromatographic unit equippedwith four linear mixed bed columns (Polymer Laboratories (20-micronparticle size)). The oven temperature is at 160° C. with the autosamplerhot zone at 160° C. and the warm zone at 145° C. The solvent is1,2,4-trichlorobenzene containing 200 ppm 2,6-di-t-butyl-4-methylphenol.The flow rate is 1.0 milliliter/minute and the injection size is 100microliters. About 0.2% by weight solutions of the samples are preparedfor injection by dissolving the sample in nitrogen purged1,2,4-trichlorobenzene containing 200 ppm 2,6-di-t-butyl-4-methylphenolfor 2.5 hrs at 160° C. with gentle mixing.

The molecular weight determination is deduced by using ten narrowmolecular weight distribution polystyrene standards (from PolymerLaboratories, EasiCal PS1 ranging from 580-7,500,000 g/mole) inconjunction with their elution volumes. The equivalent polypropylenemolecular weights are determined by using appropriate Mark-Houwinkcoefficients for polypropylene (as described by Th. G. Scholte, N. L. J.Meijerink, H. M. Schoffeleers, and A. M. G. Brands, J. Appl. Polym.Sci., 29, 3763-3782 (1984)) and polystyrene (as described by E. P.Otocka, R. J. Roe, N.Y. Hellman, P. M. Muglia, Macromolecules, 4, 507(1971)) in the Mark-Houwink equation:{N}=KM^(a)where K_(pp)=1.90E-04, a_(pp)=0.725 and K_(ps)=1.26E-04, a_(ps)=0.702.Differential Scanning Calorimetry

Differential scanning calorimetry (DSC) is a common technique that canbe used to examine the melting and crystallization of semi-crystallinepolymers. General principles of DSC measurements and applications of DSCto studying semi-crystalline polymers are described in standard texts(e.g., E. A. Turi, ed., Thermal Characterization of Polymeric Materials,Academic Press, 1981). Certain of the copolymers used in the practice ofthis invention are characterized by a DSC curve with a T_(me) thatremains essentially the same and a T_(max) that decreases as the amountof unsaturated comonomer in the copolymer is increased. T_(me) means thetemperature at which the melting ends. T_(max) means the peak meltingtemperature.

Differential Scanning Calorimetry (DSC) analysis is determined using amodel Q1000 DSC from TA Instruments, Inc. Calibration of the DSC is doneas follows. First, a baseline is obtained by running the DSC from −90°C. to 290° C. without any sample in the aluminum DSC pan. Then 7milligrams of a fresh indium sample is analyzed by heating the sample to180° C., cooling the sample to 140° C. at a cooling rate of 10° C./minfollowed by keeping the sample isothermally at 140° C. for 1 minute,followed by heating the sample from 140° C. to 180° C. at a heating rateof 10° C./min. The heat of fusion and the onset of melting of the indiumsample are determined and checked to be within 0.5° C. from 156.6° C.for the onset of melting and within 0.5 J/g from 28.71 J/g for the heatof fusion. Then deionized water is analyzed by cooling a small drop offresh sample in the DSC pan from 25° C. to −30° C. at a cooling rate of10° C./min. The sample is kept isothermally at −30° C. for 2 minutes andheated to 30° C. at a heating rate of 10° C./min. The onset of meltingis determined and checked to be within 0.5° C. from 0° C.

The polypropylene samples are pressed into a thin film at a temperatureof 190° C. About 5 to 8 mg of sample is weighed out and placed in theDSC pan. The lid is crimped on the pan to ensure a closed atmosphere.The sample pan is placed in the DSC cell and the heated at a high rateof about 100° C./min to a temperature of about 30° C. above the melttemperature. The sample is kept at this temperature for about 3 minutes.Then the sample is cooled at a rate of 10° C./min to −40° C., and keptisothermally at that temperature for 3 minutes. Consequently the sampleis heated at a rate of 10° C./min until complete melting. The resultingenthalpy curves are analyzed for peak melt temperature, onset and peakcrystallization temperatures, heat of fusion and heat ofcrystallization, T_(me), and any other DSC analyses of interest.

B-Value

“High B-value” and similar terms mean the ethylene units of a copolymerof propylene and ethylene, or a copolymer of propylene, ethylene and atleast one unsaturated comononomer, is distributed across the polymerchain in a nonrandom manner. B-values range from 0 to 2 with 1designating a perfectly random distribution of comonomer units. Thehigher the B-value, the more alternating the comonomer distribution inthe copolymer. The lower the B-value, the more blocky or clustered thecomonomer distribution in the copolymer. The high B-values of thepolymers of this invention are typically at least about 1.3, preferablyat least about 1.4, more preferably at least about 1.5 and mostpreferably at least about 1.7. The B-value is calculated as follows.

B is defined for a propylene/ethylene copolymer as:

$B = \frac{f_{({{EP} + {PE}})}}{2 \cdot F_{E} \cdot F_{P}}$where f(EP+PE)=the sum of the EP and PE diad fractions; and Fe andFp=the mole fraction of ethylene and propylene in the copolymer,respectively. B-values can be calculated for other copolymers in ananalogous manner by assignment of the respective copolymer diads. Forexample, calculation of the B-value for a propylene/1-octene copolymeruses the following equation:

$B = \frac{f_{({{OP} + {PO}})}}{2 \cdot F_{O} \cdot F_{P}}$

For propylene polymers made with a metallocene catalyst, the B-valuesare typically between 1.1 and 1.3. For propylene polymers made with aconstrained geometry catalyst, the B-values are typically between 0.9and 1.0. In contrast, the B-values of the propylene polymers of thisinvention, typically made with an activated nonmetallocene,metal-centered, heteroaryl ligand catalyst, are above about 1.4,typcially between about 1.5 and about 1.85. In turn, this means that forany P/E* copolymer, not only is the propylene block length relativelyshort for a given percentage of ethylene but very little, if any, longsequences of 3 or more sequential ethylene insertions are present in thecopolymer, unless the ethylene content of the polymer is very high. FIG.1 and the data of the following tables are illustrative. The catalystsare activated nonmetallocene, metal-centered, heteroaryl ligandcatalysts, and these made P/E* polymers. The Catalyst E is a metallocenecatalyst, and it did not make the P/E* polymers. Interestingly, theB-values of the P/E* polymers remained high even for polymers withrelatively large amounts, e.g., >30 mole %, ethylene.

TABLE A B-Values of Selected Propylene Polymers Regio-errors 14-16 ppm(mole %) MFR Density Ethylene (average of Tmax Cryst. (%) Tg NumberDescription (g/10 min) (kg/dm 3#) (mol %) two) B (° C.) (from Hf) (° C.)A-1 P/E* via 25.8 0.8864 10.6 0.00 1.40 104.7 37.3 −20.9 Catalyst I A-2HPP via 1.9 0.8995 0.0 1.35 None 139.5 48.7 −6.9 Catalyst G A-3 P/E* via1.7 0.8740 11.8 0.24 1.67 63.3 24.4 −23.6 Catalyst G A-4 P/E* via 1.50.8703 12.9 0.32 1.66 57.7 21.9 −24.5 Catalyst G A-5 HPP via 2.5 0.90210.0 1.18 None 143.5 61.4 −6.0 Catalyst H A-6 P/E* via 1.9 0.8928 4.30.57 1.77 120.6 48.3 −13.8 Catalyst H A-7 P/E* via 2.2 0.8850 8.2 0.471.71 96.0 40.5 −19.3 Catalyst H A-8 P/E* via 2.3 0.8741 11.8 0.34 1.7967.9 27.4 −23.7 Catalyst H A-9 P/E* via 2 0.8648 15.8 0.24 1.67 53.710.5 −27.6 Catalyst H A-10 P/E* via 2.0 0.8581 18.6 0.18 1.70 none 2.6−29.9 Catalyst H Catalyst I isdimethyleamidoborane-bis-η⁵-(2-methyl-4-napthylinden-1-yl)zirconiumη⁴-1,4,-dipheny-1,3-butadiene. HPP means polypropylene homopolymer.Catalysts G, H and I are illustrated in FIGS. 10G, 10H and 10I,respectively.

TABLE B B-Values of Selected Propylene/Ethylene Copolymers Regio-errors14-16 ppm (mole %) Ethylene (average of Cryst. (%) Number Description(mol %) two) B Tmax (° C.) (from Hf) Tg (° C.) B-1 P/E* via 1.6 0.371.78 138.2 53.9 −8.1 Catalyst H B-2 P/E* via 7.7 0.38 1.66 105.6 38.9−18.5 Catalyst H B-3 P/E* via 7.8 0.41 1.61 107.7 39.6 −18.2 Catalyst HB-4 P/E* via 12.3 0.31 1.58 74.7 30.7 −22.5 Catalyst H B-5 P/E* via 14.80.21 1.67 90.6 31.2 −22.9 Catalyst H B-6 P/E* via 12.4 0.31 1.61 67.420.8 −26.8 Catalyst H B-7 P/E* via 14.7 0.30 1.60 78.1 19.9 −25.9Catalyst H B-8 P/E* via 33.7 0.00 1.67 None 0.0 −39.2 Catalyst H B-9P/E* via 31.3 0.00 1.67 None 0.0 −39.2 Catalyst H B-10 P/E* via 12.00.25 1.61 72.4 33.2 −22.8 Catalyst J B-11 P/E* via 8.9 0.37 1.63 91.440.1 −19.8 Catalyst J B-12 P/E* via 8.5 0.44 1.68 101.7 38.7 −20.0Catalyst J B-13 P/E* via 7.6 0.47 1.68 107.6 43.2 −18.8 Catalyst J B-14P/E* via 7.6 0.35 1.64 106.2 42.4 −18.5 Catalyst J B-15 P/E* via 8.60.33 1.64 104.4 41.0 −19.5 Catalyst J B-16 P/E* via 9.6 0.35 1.65 85.538.1 −20.6 Catalyst J B-17 P/E* via 8.6 0.37 1.63 104.1 41.8 −19.6Catalyst J B-18 P/E* via 8.6 0.34 1.62 90.8 40.8 −19.6 Catalyst J B-19P/E* via 8.6 0.40 1.58 93.3 41.9 −19.2 Catalyst J Catalyst J isillustrated in FIG. 10J.

The processes used to produce the crystallizable propylene polymers usedin the practice of this invention can be used to produce propyleneinterpolymers of ethylene and optionally C₄-C₂₀ alpha-olefins having arelatively broad melting point in a DSC heating curve. While not wishingto be held to any particular theory of operation, it is believed thatthe high B values for the P/E* interpolymers and the process for theirmanufacture lead to an ethylene distribution within the polymer chainsthat leads to a broad melting behavior. In FIGS. 2A and 2B, for example,a relatively narrow melting peak is observed for a propylene/ethylenecopolymer prepared using a metallocene as a comparative example(Comparative Example 1), while the melting peak for a similar P/E*copolymer exhibits a broad melting point. Such broad melting behavior isuseful in applications requiring, for example, a relatively low heatseal initiation temperature, or a broad hot tack and/or heat sealwindow.

Thermal Properties

FIGS. 3 and 4 further illustrate the thermal properties of the P/E*polymers used in the practice of this invention. FIG. 3 illustrates thatthe P/E* polymers have a higher glass transition temperature (Tg) thando comparable metallocene-catalysed propylene polymers at a equivalentcrystallinity. This means that the P/E* copolymers are likely to exhibitbetter creep resistance than conventional metallocene-catalyzedpropylene copolymers. Moreover, the T_(max) data of Table A shows thatthe P/E* copolymers have a lower melting point at the same crystallinityas a metallocene-catalyzed propylene copolymer. This, in turn, meansthat the P/E* polymers are likely to process better (e.g., require lessheating) than conventional metallocene-catalyzed propylene polymers.

FIG. 4 illustrates that the P/E* polymers also have a lower Tg at anequivalent ethylene content than a propylene polymer made with aconstrained geometry catalyst (CGC) and this, in turn, means that theP/E* polymers are likely to exhibit better low temperature toughnessthan the CGC propylene polymers making the P/E* polymers attractivecandidates for food packaging applications.

Temperature-Rising Elution Fractionation

The determination of crystallizable sequence length distribution can beaccomplished on a preparative scale by temperature-rising elutionfractionation (TREF). The relative mass of individual fractions can beused as a basis for estimating a more continuous distribution. L. Wild,et al., Journal of Polymer Science: Polymer. Physics Ed., 20, 441(1982), scaled down the sample size and added a mass detector to producea continuous representation of the distribution as a function of elutiontemperature. This scaled down version, analytical temperature-risingelution fractionation (ATREF), is not concerned with the actualisolation of fractions, but with more accurately determining the weightdistribution of fractions.

While TREF was originally applied to copolymers of ethylene and higherα-olefins, it can also be used for the analysis of copolymers ofpropylene with ethylene (or higher α-olefins). The analysis ofcopolymers of propylene requires higher temperatures for the dissolutionand crystallization of pure, isotactic polypropylene, but most of thecopolymerization products of interest elute at similar temperatures asobserved for copolymers of ethylene. The following table is a summary ofconditions used for the analysis of copolymers of propylene. Except asnoted the conditions for TREF are consistent with those of Wild, et al.,ibid, and Hazlitt, Journal of Applied Polymer Science: Appl. Polym.Symp., 45, 25(1990).

TABLE C Parameters Used for TREF Parameter Explanation Column type andsize Stainless steel shot with 1.5 cc interstitial volume Mass detectorSingle beam infrared detector at 2920 cm⁻¹ Injection temperature 150° C.Temperature control device GC oven Solvent 1,2,4-trichlorobenzeneConcentration 0.1 to 0.3% (weight/weight) Cooling Rate 1 140° C. to 120°C. @ −6.0° C./min. Cooling Rate 2 120° C. to 44.5° C. @ −0.1° C./min.Cooling Rate 3 44.5° C. to 20° C. @ −0.3° C./min. Heating Rate 20° C. to140° C. @ 1.8° C./min. Data acquisition rate 12/min.

The data obtained from TREF are expressed as a normalized plot of weightfraction as a function of elution temperature. The separation mechanismis analogous to that of copolymers of ethylene, whereby the molarcontent of the crystallizable component (ethylene) is the primary factorthat determines the elution temperature. In the case of copolymers ofpropylene, it is the molar content of isotactic propylene units thatprimarily determines the elution temperature. FIG. 5 is a representationof the typical type of distribution one would expect for apropylene/ethylene copolymer made with a metallocene polymer and anexample of a P/E* copolymer.

The shape of the metallocene curve in FIG. 5 is typical for ahomogeneous copolymer. The shape arises from the inherent, randomincorporation of comonomer. A prominent characteristic of the shape ofthe curve is the tailing at lower elution temperature compared to thesharpness or steepness of the curve at the higher elution temperatures.A statistic that reflects this type of assymetry is skewness. Equation 1mathematically represents the skewness index, S_(ix), as a measure ofthis asymmetry.

$\begin{matrix}{S_{ix} = {\frac{\sqrt[3]{\sum{w_{i}*\left( {T_{i} - T_{Max}} \right)^{3}}}}{\sqrt{\sum{w_{i}*\left( {T_{i} - T_{Max}} \right)^{2}}}}.}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

The value, T_(Max), is defined as the temperature of the largest weightfraction eluting between 50 and 90° C. in the TREF curve. T_(i) andw_(i) are the elution temperature and weight fraction respectively of anarbitrary, i^(th) fraction in the TREF distribution. The distributionshave been normalized (the sum of the w_(i) equals 100%) with respect tothe total area of the curve eluting above 30° C. Thus, the indexreflects only the shape of the crystallized polymer and anyuncrystallized polymer (polymer still in solution at or below 30° C.)has been omitted from the calculation shown in Equation 1.

Polymer Definitions and Descriptions

“Polymer” means a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, although it is often usedinterchangeably with “interpolymer” to refer to polymers made from threeor more different types of monomers or comonomers), terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike. The terms “monomer” or “comonomer” are used interchangeably, andthey refer to any compound with a polymerizable moiety which is added toa reactor in order to produce a polymer. In those instances in which apolymer is described as comprising one or more monomers, e.g., a polymercomprising propylene and ethylene, the polymer, of course, comprisesunits derived from the monomers, e.g., —CH₂—CH₂—, and not the monomeritself, e.g., CH₂═CH₂.

“Metallocene-catalyzed polymer” or similar term means any polymer thatis made in the presence of a metallocene catalyst. “Constrained geometrycatalyst catalyzed polymer”, “CGC-catalyzed polymer” or similar termmeans any polymer that is made in the presence of a constrained geometrycatalyst. “Ziegler-Natta-catalyzed polymer”, Z-N-catalyzed polymer” orsimilar term means any polymer that is made in the presence of aZiegler-Natta catalyst. “Metallocene” means a metal-containing compoundhaving at least one substituted or unsubstituted cyclopentadienyl groupbound to the metal. “Constrained geometry catalyst” or “CGC” as hereused has the same meaning as this term is defined and described in U.S.Pat. Nos. 5,272,236 and 5,278,272.

“Random copolymer” means a copolymer in which the monomer is randomlydistributed across the polymer chain.

“Propylene homopolymer” and similar terms mean a polymer consistingsolely or essentially all of units derived from propylene.“Polypropylene copolymer” and similar terms mean a polymer comprisingunits derived from propylene and ethylene and/or one or more unsaturatedcomonomers. The term “copolymer” includes terpolymers, tetrapolymers,etc.

The unsaturated comonomers used in the practice of this inventioninclude, C₄₋₂₀ α-olefins, especially C₄₋₁₂ α-olefins such as 1-butene,1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,1-dodecene and the like; C₄₋₂₀ diolefins, preferably 1,3-butadiene,1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) anddicyclopentadiene; C₈₋₄₀ vinyl aromatic compounds including sytrene, o-,m-, and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnapthalene;and halogen-substituted C₈₋₄₀ vinyl aromatic compounds such aschlorostyrene and fluorostyrene. For purposes of this invention,ethylene and propylene are not included in the definition of unsaturatedcomonomers.

The propylene copolymers used in the practice of this inventiontypically comprise units derived from propylene in an amount of at leastabout 60, preferably at least about 80 and more preferably at leastabout 85, wt % of the copolymer. The typical amount of units derivedfrom ethylene in propylene/ethylene copolymers is at least about 0.1,preferably at least about 1 and more preferably at least about 5 wt %,and the maximum amount of units derived from ethylene present in thesecopolymers is typically not in excess of about 35, preferably not inexcess of about 30 and more preferably not in excess of about 20, wt %of the copolymer. The amount of units derived from the unsaturatedcomonomer(s), if present, is typically at least about 0.01, preferablyat least about 1 and more preferably at least about 5, wt %, and thetypical maximum amount of units derived from the unsaturatedcomonomer(s) typically does not exceed about 35, preferably it does notexceed about 30 and more preferably it does not exceed about 20, wt % ofthe copolymer. The combined total of units derived from ethylene and anyunsaturated comonomer typically does not exceed about 40, preferably itdoes not exceed about 30 and more preferably it does not exceed about20, wt % of the copolymer.

The copolymers used in the practice of this invention comprisingpropylene and one or more unsaturated comonomers (other than ethylene)also typically comprise units derived from propylene in an amount of atleast about 60, preferably at least about 70 and more preferably atleast about 80, wt % of the copolymer. The one or more unsaturatedcomonomers of the copolymer comprise at least about 0.1, preferably atleast about 1 and more preferably at least about 3, weight percent, andthe typical maximum amount of unsaturated comonomer does not exceedabout 40, and preferably it does not exceed about 30, wt % of thecopolymer.

¹³C NMR

The P/E* polymers used in the practice of this invention are furthercharacterized as having substantially isotactic propylene sequences.“Substantially isotactic propylene sequences” and similar terms meanthat the sequences have an isotactic triad (mm) measured by ¹³C NMR ofgreater than about 0.85, preferably greater than about 0.90, morepreferably 0greater than about 0.92 and most preferably greater thanabout 0.93. Isotactic triads are well known in the art and are describedin, for example, U.S. Pat. No. 5,504,172 and WO 00/01745 which refer tothe isotactic sequence in terms of a triad unit in the copolymermolecular chain determined by ¹³C NMR spectra. The NMR spectra aredetermined as follows.

¹³C NMR spectroscopy is one of a number of techniques known in the artof measuring comonomer incorporation into a polymer. An example of thistechnique is described for the determination of comonomer content forethylene/α-olefin copolymers in Randall (Journal of MacromolecularScience, Reviews in Macromolecular Chemistry and Physics, C29 (2 & 3),201-317 (1989)). The basic procedure for determining the comonomercontent of an olefin interpolymer involves obtaining the ¹³C NMRspectrum under conditions where the intensity of the peaks correspondingto the different carbons in the sample is directly proportional to thetotal number of contributing nuclei in the sample. Methods for ensuringthis proportionality are known in the art and involve allowance forsufficient time for relaxation after a pulse, the use ofgated-decoupling techniques, relaxation agents, and the like. Therelative intensity of a peak or group of peaks is obtained in practicefrom its computer-generated integral. After obtaining the spectrum andintegrating the peaks, those peaks associated with the comonomer areassigned. This assignment can be made by reference to known spectra orliterature, or by synthesis and analysis of model compounds, or by theuse of isotopically labeled comonomer. The mole % comonomer can bedetermined by the ratio of the integrals corresponding to the number ofmoles of comonomer to the integrals corresponding to the number of molesof all of the monomers in the interpolymer, as described in Randall, forexample.

The data is collected using a Varian UNITY Plus 400 MHz NMRspectrometer, corresponding to a ¹³C resonance frequency of 100.4 MHz.Acquisition parameters are selected to ensure quantitative ¹³C dataacquisition in the presence of the relaxation agent. The data isacquired using gated ¹H decoupling, 4000 transients per data file, a 7sec pulse repetition delay, spectral width of 24,200 Hz and a file sizeof 32K data points, with the probe head heated to 130° C. The sample isprepared by adding approximately 3 mL of a 50/50 mixture oftetrachloroethane-d2/orthodichlorobenzene that is 0.025M in chromiumacetylacetonate (relaxation agent) to 0.4 g sample in a 10 mm NMR tube.The headspace of the tube is purged of oxygen by displacement with purenitrogen. The sample is dissolved and homogenized by heating the tubeand its contents to 150° C. with periodic refluxing initiated by heatgun.

Following data collection, the chemical shifts are internally referencedto the mmmm pentad at 21.90 ppm.

For propylene/ethylene copolymers, the following procedure is used tocalculate the percent ethylene in the polymer. Integral regions aredetermined as follows:

TABLE D Integral Regions for Determining % Ethylene Region Designationppm A 44-49 B 36-39 C 32.8-34   P 31.0-30.8 Q Peak at 30.4 R Peak at 30F 28.0-29.7 G   26-28.3 H 24-26 I 19-23Region D is calculated as D=P×(G×Q)/2. Region E=R+Q+(G×Q)/2.

TABLE E Calculation of Region D PPP = (F + A − 0.5 D)/2 PPE = D EPE = CEEE = (E − 0.5 G)/2 PEE = G PEP = H Moles P = sum P centered triadsMoles E = sum E centered triads Moles P = (B + 2A)/2 Moles E = (E + G +0.5B + H)/2

C2 values are calculated as the average of the two methods above (triadsummation and algebraic) although the two do not usually vary.

The mole fraction of propylene insertions resulting in regio-errors iscalculated as one half of the sum of the two of methyls showing up at14.6 and 15.7 ppm divided by the total methyls at 14-22 ppm attributableto propylene. The mole percent of the regio-error peaks is the molefraction times 100.

Isotacticity at the triad level (mm) is determined from the integrals ofthe mm triad (22.70-21.28 ppm), the mr triad (21.28-20.67 ppm) and therr triad (20.67-19.74). The mm isotacticity is determined by dividingthe intensity of the mm triad by the sum of the mm, mr, and rr triads.For ethylene copolymers the mr region is corrected by subtracting37.5-39 ppm integral. For copolymers with other monomers that producepeaks in the regions of the mm, mr, and rr triads, the integrals forthese regions are similarly corrected by subtracting the intensity ofthe interfering peak using standard NMR techniques, once the peaks havebeen identified. This can be accomplished, for example, by analysis of aseries of copolymers of various levels of monomer incorporation, byliterature assignments, by isotopic labeling, or other means which areknown in the art.

The ¹³C NMR peaks corresponding to a regio-error at about 14.6 and about15.7 ppm are believed to be the result of stereoselective 2,1-insertionerrors of propylene units into the growing polymer chain. In a typicalP/E* polymer, these peaks are of about equal intensity, and theyrepresent about 0.02 to about 7 mole percent of the propylene insertionsinto the homopolymer or copolymer chain. For some embodiments, theyrepresent about 0.005 to about 20 mole % or more of the propyleneinsertions. In general, higher levels of regio-errors lead to a loweringof the melting point and the modulus of the polymer, while lower levelslead to a higher melting point and a higher modulus of the polymer.

The nature and level of comonomers other than propylene also control themelting point and modulus of the copolymer. In any particularapplication, it may be desirable to have either a high or low meltingpoint or a high or low modulus modulus. The level of regio-errors can becontrolled by several means, including the polymerization temperature,the concentration of propylene and other monomers in the process, thetype of (co)monomers, and other factors. Various individual catalyststructures may inherently produce more or less regio-errors than othercatalysts. For example, in Table A above, the propylene homopolymerprepared with Catalyst G has a higher level of regio-errors and a lowermelting point than the propylene homopolymer prepared with Catalyst H,which has a higher melting point. If a higher melting point (or highermodulus) polymer is desired, then it is preferable to have fewerregio-errors than about 3 mole % of the propylene insertions, morepreferably less than about 1.5 mole % of the propylene insertions, stillmore preferably less than about 1.0 mole % of the propylene insertions,and most preferably less than about 0.5 mole % of the propyleneinsertions. If a lower melting point (or modulus) polymer is desired,then it is preferable to have more regio-errors than about 3 mole % ofthe propylene insertions, more preferably more than about 5 mole % ofthe propylene insertions, still more preferably more than about 6 mole %of the propylene insertions, and most preferably more than about 10 mole% of the propylene insertions.

Those skilled artisan will appreciate that the mole % of regio-errorsfor a P/E* polymer which is a component of a blend refers to the mole %of regio-errors of the particular P/E* polymer component of the blend,and not as a mole % of the overall blend.

The comparison of several ¹³C NMR sprectra further illustrates theunique regio-errors of the P/E* polymers. FIGS. 6 and 7 are the spectraof the propylene homopolymer products of Examples 7 and 8, respectively,each made with an activated nonmetallocene, metal-centered, heteroarylligand catalyst. The spectrum of each polymer reports a high degree ofisotacticity and the unique regio-errors of these inventive polymers.FIG. 8 is the ¹³C NMR spectrum of the propylene-ethylene copolymer ofExample 2, made with the same catalyst used to make the propylenehomopolymer of Example 7, and it too reports a high degree ofisotacticity and the same regio-errors of the propylene homopolymers ofFIG. 9. The presence of the ethylene comonomer does not preclude theoccurrence of these unique regio-errors. The ¹³C NMR spectrum of FIG. 9is that of the propylene-ethylene copolymer product of ComparativeExample 1 which was prepared using a metallocene catalyst. This spectrumdoes not report the regio-error (around 15 ppm) characteristic of theP/E* polymers.

Melt Flow Rate (MFR)

The propylene homo- and copolymers used in the practice of thisinvention typically have an MFR of at least about 0.01, preferably atleast about 0.05, more preferably at least about 0.1 and most preferablyat least about 0.2. The maximum MFR typically does not exceed about1,000, preferably it does not exceed about 500, more preferably it doesnot exceed about 100, more preferably it does not exceed about 80 andmost preferably it does not exceed about 50. The MFR for propylenehomopolymers and copolymers of propylene and ethylene and/or one or moreC₄-C₂₀ α olefins is measured according to ASTM D-1238, condition L (2.16kg, 230 degrees C.).

Propylene Copolymers

The propylene copolymers used in the practice of this invention that areof particular interest include propylene/ethylene, propylene/1-butene,propylene/1-hexene, propylene/4-methyl-1-pentene, propylene/1-octene,propylene/ethylene/1-butene, propylene/ethylene/ENB,propylene/ethylene/1-hexene, propylene/ethylene/1-octene,propylene/styrene, and propylene/ethylene/styrene.

Catalyst Definitions and Descriptions

The P* and P/E* polymers used in the practice of this invention are madeusing a metal-centered, heteroaryl ligand catalyst in combination withone or more activators, e.g., an alumoxane. In certain embodiments, themetal is one or more of hafnium and zirconium.

More specifically, in certain embodiments of the catalyst, the use of ahafnium metal has been-found to be preferred as compared to a zirconiummetal for heteroaryl ligand catalysts. A broad range of ancillary ligandsubstituents may accommodate the enhanced catalytic performance. Thecatalysts in certain embodiments are compositions comprising the ligandand metal precursor, and, optionally, may additionally include anactivator, combination of activators or activator package.

The catalysts used to make the P* and P/E* polymers additionally includecatalysts comprising ancillary ligand-hafnium complexes, ancillaryligand-zirconium complexes and optionally activators, which catalyzepolymerization and copolymerization reactions, particularly withmonomers that are olefins, diolefins or other unsaturated compounds.Zirconium complexes, hafnium complexes, compositions or compounds usingthe disclosed ligands are within the scope of the catalysts useful inthe practice of this invention. The metal-ligand complexes may be in aneutral or charged state. The ligand to metal ratio may also vary, theexact ratio being dependent on the nature of the ligand and metal-ligandcomplex. The metal-ligand complex or complexes may take different forms,for example, they may be monomeric, dimeric or of an even higher order.

“Nonmetallocene” means that the metal of the catalyst is not attached toa substituted or unsubstituted cyclopentadienyl ring. Representativenonmetallocene, metal-centered, heteroaryl ligand catalysts aredescribed in US Patent Application Publication Nos. 2002/0142912;2002/0137845 and U.S. Pat. Nos. 6,750,345; 6,713,577; 6,706,829 and6,727,361.

As here used, “nonmetallocene, metal-centered, heteroaryl ligandcatalyst” means the catalyst derived from the ligand described informula I. As used in this phrase, “heteroaryl” includes substitutedheteroaryl.

As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, e.g., R¹, R²R³, R⁴, and R⁵ can be identicalor different (e.g. R¹, R², R³, R⁴, and R⁵ may all be substituted alkylsor R¹ and R² may be a substituted alkyl and R³ may be an aryl, etc.).Use of the singular includes use of the plural and vice versa (e.g., ahexane solvent, includes hexanes). A named R group will generally havethe structure that is recognized in the art as corresponding to R groupshaving that name. The terms “compound” and “complex” are generally usedinterchangeably in this specification, but those of skill in the art mayrecognize certain compounds as complexes and vice versa. For thepurposes of illustration, representative certain groups are definedherein. These definitions are intended to supplement and illustrate, notpreclude, the definitions known to those of skill in the art.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 toabout 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including branched or unbranched,saturated or unsaturated species, such as alkyl groups, alkenyl groups,aryl groups, and the like. “Substituted hydrocarbyl” refers tohydrocarbyl substituted with one or more substituent groups, and theterms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” referto hydrocarbyl in which at least one carbon atom is replaced with aheteroatom.

The term “alkyl” is used herein to refer to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Suitable alkylradicals include, for example, methyl, ethyl, n-propyl, i-propyl,2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl), etc. In particular embodiments, alkyls have between 1and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20carbon atoms.

“Substituted alkyl” refers to an alkyl as just described in which one ormore hydrogen atom bound to any carbon of the alkyl is replaced byanother group such as a halogen, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,halogen, alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

The term “heteroalkyl” refers to an alkyl as described above in whichone or more carbon atoms to any carbon of the alkyl is replaced by aheteroatom selected from the group consisting of N, O, P, B, S, Si, Sb,Al, Sn, As, Se and Ge. This same list of heteroatoms is usefulthroughout this specification. The bond between the carbon atom and theheteroatom may be saturated or unsaturated. Thus, an alkyl substitutedwith a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, or seleno is within the scope of the term heteroalkyl. Suitableheteroalkyls include cyano, benzoyl, 2-pyridyl, 2-furyl and the like.

The term “cycloalkyl” is used herein to refer to a saturated orunsaturated cyclic non-aromatic hydrocarbon radical having a single ringor multiple condensed rings. Suitable cycloalkyl radicals include, forexample, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc. Inparticular embodiments, cycloalkyls have between 3 and 200 carbon atoms,between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.

“Substituted cycloalkyl” refers to cycloalkyl as just describedincluding in which one or more hydrogen atom to any carbon of thecycloalkyl is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substituted cycloalkylradicals include, for example, 4-dimethylaminocyclohexyl,4,5-dibromocyclohept-4-enyl, and the like.

The term “heterocycloalkyl” is used herein to refer to a cycloalkylradical as described, but in which one or more or all carbon atoms ofthe saturated or unsaturated cyclic radical are replaced by a heteroatomsuch as nitrogen, phosphorous, oxygen, sulfur, silicon, germanium,selenium, or boron. Suitable heterocycloalkyls include, for example,piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl,piperidinyl, pyrrolidinyl, oxazolinyl and the like.

“Substituted heterocycloalkyl” refers to heterocycloalkyl as justdescribed including in which one or more hydrogen atom to any atom ofthe heterocycloalkyl is replaced by another group such as a halogen,alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substitutedheterocycloalkyl radicals include, for example, N-methylpiperazinyl,3-dimethylaminomorpholinyl and the like.

The term “aryl” is used herein to refer to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. In particularembodiments, aryls have between 1 and 200 carbon atoms, between 1 and 50carbon atoms or between 1 and 20 carbon atoms.

“Substituted aryl” refers to aryl as just described in which one or morehydrogen atom bound to any carbon is replaced by one or more functionalgroups such as alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen,alkylhalos (e.g., CF₃), hydroxy, amino, phosphido, alkoxy, amino, thio,nitro, and both saturated and unsaturated cyclic hydrocarbons which arefused to the aromatic ring(s), linked covalently or linked to a commongroup such as a methylene or ethylene moiety. The common linking groupmay also be a carbonyl as in benzophenone or oxygen as in diphenyletheror nitrogen in diphenylamine.

The term “heteroaryl” as used herein refers to aromatic or unsaturatedrings in which one or more carbon atoms of the aromatic ring(s) arereplaced by a heteroatom(s) such as nitrogen, oxygen, boron, selenium,phosphorus, silicon or sulfur. Heteroaryl refers to structures that maybe a single aromatic ring, multiple aromatic ring(s), or one or morearomatic rings coupled to one or more non-aromatic ring(s). Instructures having multiple rings, the rings can be fused together,linked covalently, or linked to a common group such as a methylene orethylene moiety. The common linking group may also be a carbonyl as inphenyl pyridyl ketone. As used herein, rings such as thiophene,pyridine, isoxazole, pyrazole, pyrrole, furan, etc. or benzo-fusedanalogues of these rings are defined by the term “heteroaryl.”

“Substituted heteroaryl” refers to heteroaryl as just describedincluding in which one or more hydrogen atoms bound to any atom of theheteroaryl moiety is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio,seleno and combinations thereof. Suitable substituted heteroarylradicals include, for example, 4-N,N-dimethylaminopyridine.

The term “alkoxy” is used herein to refer to the —OZ¹ radical, where Z¹is selected from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substitutedheterocycloalkyl, silyl groups and combinations thereof as describedherein. Suitable alkoxy radicals include, for example, methoxy, ethoxy,benzyloxy, t-butoxy, etc. A related term is “aryloxy” where Z¹ isselected from the group consisting of aryl, substituted aryl,heteroaryl, substituted heteroaryl, and combinations thereof. Examplesof suitable aryloxy radicals include phenoxy, substituted phenoxy,2-pyridinoxy, 8-quinalinoxy and the like.

As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical, whereeach of Z¹, Z², and Z³ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinationsthereof.

As used herein the term “boryl” refers to the —BZ¹Z² group, where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.

As used herein, the term “phosphino” refers to the group —PZ¹Z², whereeach of Z¹ and Z² is independently selected from the group consisting ofhydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

As used herein, the term “phosphine” refers to the group :PZ¹Z²Z³, whereeach of Z¹, Z³ and Z² is independently selected from the groupconsisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

The term “amino” is used herein to refer to the group —NZ¹Z², where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl andcombinations thereof.

The term “amine” is used herein to refer to the group :NZ¹Z²Z³, whereeach of Z¹, Z² and Z² is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl (including pyridines), substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “thio” is used herein to refer to the group —SZ¹, where Z¹ isselected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “seleno” is used herein to refer to the group —SeZ¹, where Z¹is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “saturated” refers to lack of double and triple bonds betweenatoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, andthe like.

The term “unsaturated” refers to the presence one or more double and/ortriple bonds between atoms of a radical group such as vinyl, acetylide,oxazolinyl, cyclohexenyl, acetyl and the like.

Ligands

Suitable ligands useful in the catalysts used to make the P* and P/E*polymers used in the practice of this invention can be characterizedbroadly as monoanionic ligands having an amine and a heteroaryl orsubstituted heteroaryl group. The ligands of these catalysts arereferred to, for the purposes of this invention, as nonmetalloceneligands, and may be characterized by the following general formula:

wherein R¹ is very generally selected from the group consisting ofalkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl and combinations thereof. In many embodiments, R¹ is a ringhaving from 4-8 atoms in the ring generally selected from the groupconsisting of substituted cycloalkyl, substituted heterocycloalkyl,substituted aryl and substituted heteroaryl, such that R¹ may becharacterized by the general formula:

where Q¹ and Q⁵ are substituents on the ring ortho to atom E, with Ebeing selected from the group consisting of carbon and nitrogen and withat least one of Q¹ or Q⁵ being bulky (defined as having at least 2atoms). Q¹ and Q⁵ are independently selected from the group consistingof alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl,substituted aryl and silyl, but provided that Q¹ and Q⁵ are not bothmethyl. Q″_(q) represents additional possible substituents on the ring,with q being 1, 2, 3, 4 or 5 and Q″ being selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, halide, nitro, and combinations thereof.T is a bridging group selected group consisting of —CR²R³— and —SiR²R³—with R² and R³ being independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, halide, nitro, and combinations thereof. J″ is generallyselected from the group consisting of heteroaryl and substitutedheteroaryl, with particular embodiments for particular reactions beingdescribed herein.

In a more specific embodiment, suitable nonmetallocene ligands may becharacterized by the following general formula:

wherein R¹ and T are as defined above and each of R⁴, R⁵, R⁶ and R⁷ isindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl,aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof. Optionally, any combination of R¹, R², R³ andR⁴ may be joined together in a ring structure.

In certain more specific embodiments, the ligands may be characterizedby the following general formula:

wherein Q¹, Q⁵, R², R³, R⁴, R⁵, R⁶ and R⁷ are as defined above. Q², Q³and Q⁴ are independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedhetercycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio,seleno, nitro, and combinations thereof.

In other more specific embodiments, the suitable ligands may becharacterized by the following general formula:

wherein R¹, R³, R⁴, R¹, R⁵, and R⁶ are as defined above. In thisembodiment the R⁷ substituent has been replaced with an aryl orsubstituted aryl group, with R¹⁰, R¹¹, R¹² and R¹³ being independentlyselected from the group consisting of hydrogen, halo, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3-50 non-hydrogen atoms.R¹⁴ is selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro,and combinations thereof.

In still more specific embodiments, the ligands may be characterized bythe general formula:

wherein R²-R⁶, R¹⁰-R¹⁴ and Q¹-Q⁵ are all as defined above.

In certain embodiments, R² is preferably hydrogen. Also preferably, eachof R⁴ and R⁵ is hydrogen and R⁶ is either hydrogen or is joined to R⁷ toform a fused ring system. Also preferred is where R³ is selected fromthe group consisting of benzyl, phenyl, 2-biphenyl, t-butyl,2-dimethylaminophenyl (2-(NMe₂)—C₆H₄—),2-methoxyphenyl (2-MeO—C₆H₄—),anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl,9-phenanthrenyl. Also preferred is where R¹ is selected from the groupconsisting of mesityl, 4-isopropylphenyl (4-Pr^(i)—C₆H₄—), napthyl,3,5-(CF₃)₂—C₆H₃—, 2-Me-napthyl, 2,6-(Pr^(i))₂—C₆H₃—, 2-biphenyl,2-Me-4-MeO—C₆H₃—; 2-Bu^(t)—C₆H₄—, 2,5-(Bu^(t))₂—C₆H₃—,2-Pr^(i)-6-Me-C₆H₃—; 2-Bu^(t)-6-Me-C₆H₃—, 2,6-Et₂-C₆H₃—,2-sec-butyl-6-Et—C₆H₃— Also preferred is where R⁷ is selected from thegroup consisting of hydrogen, phenyl, napthyl, methyl, anthracenyl,9-phenanthrenyl, mesityl, 3,5-(CF₃)₂—C₆H₃—, 2-CF₃—C₆H₄—, 4-CF₃—C₆H₄—,3,5-F₂—C₆H₃—, 4-F—C₆H₄—, 2,4-F₂—C₆H₃—, 4-(NMe₂)—C₆H₄—, 3-MeO—C₆H₄—,4-MeO—C₆H₄—, 3,5-Me₂-C₆H₃—, o-tolyl, 2,6-F₂—C₆H₃— or where R⁷ is joinedtogether with R⁶ to form a fused ring system, e.g., quinoline.

Also optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joined to forma fused ring system having from 3-50 non-hydrogen atoms in addition tothe pyridine ring, e.g. generating a quinoline group. In theseembodiments, R³ is selected from the group consisting of aryl,substituted aryl, heteroaryl, substituted heteroaryl, primary andsecondary alkyl groups, and —PY₂ where Y is selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.

Optionally within above formulas IV and V, R⁶ and R¹⁰ may be joined toform a ring system having from 5-50 non-hydrogen atoms. For example, ifR⁶ and R¹⁰ together form a methylene, the ring will have 5 atoms in thebackbone of the ring, which may or may not be substituted with otheratoms. Also for example, if R⁶ and R¹⁰ together form an ethylene, thering will have 6 atoms in the backbone of the ring, which may or may notbe substituted with other atoms. Substituents from the ring can beselected from the group consisting of halo, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof.

In certain embodiments, the ligands are novel compounds. One example ofthe novel ligand compounds, includes those compounds generallycharacterized by formula (III), above where R² is selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, aryl, and substituted aryl; and R³ is aphosphino characterized by the formula —PZ¹Z², where each of Z¹ and Z²is independently selected from the group consisting of hydrogen,substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, silyl, alkoxy,aryloxy, amino and combinations thereof. Particularly preferredembodiments of these compounds include those where Z¹ and Z² are eachindependently selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, heterocycloalkyl, aryl, and substituted aryl; andmore specifically phenyl; where Q¹, Q³, and Q⁵ are each selected fromthe group consisting of alkyl and substituted alkyl and each of Q² andQ⁴ is hydrogen; and where R⁴, R⁵, R⁶ and R⁷ are each hydrogen.

The ligands may be prepared using known procedures. See, for example,Advanced Organic Chemistry, March, Wiley, New York 1992 (4^(th) Ed.).Specifically, the ligands of the invention may be prepared using the twostep procedure outlined in Scheme 1.

In Scheme 1, the * represents a chiral center when R² and R³ are notidentical; also, the R groups have the same definitions as above.Generally, R³M² is a nucleophile such as an alkylating or arylating orhydrogenating reagent and M² is a metal such as a main group metal, or ametalloid such as boron. The alkylating, arylating or hydrogenatingreagent may be a Grignard, alkyl, aryl-lithium or borohydride reagent.Scheme 1, step 2 first employs the use of complexing reagent.Preferably, as in the case of Scheme 1, magnesium bromide is used as thecomplexing reagent. The role of the complexing reagent is to direct thenucleophile, R³M², selectively to the imine carbon. Where the presenceof functional groups impede this synthetic approach, alternativesynthetic strategies may be employed. For instance, ligands whereR³=phosphino can be prepared in accordance with the teachings of U.S.Pat. Nos. 6,034,240 and 6,043,363. In addition, tetra-alkylhafniumcompounds or tetra-substituted alkylhafnium compounds ortetra-arylhafnium compounds or tetra-substituted arylhafnium compoundsmay be employed in step 2, in accordance with the teachings of U.S. Pat.No. 6,103,657. Scheme 2 further describes a synthesis process:

In scheme 2, h=1 or 2 and the bromine ions may or may not be bound tothe magnesium. The effect of the complexation is to guide the subsequentnucleophilic attack by R³M² to the imine carbon. As shown in Scheme 2 bythe *, where R² and R³ are different, this approach also leads to theformation of a chiral center on the ancillary ligands of the inventionwhich promotes resin tacitity. Under some circumstances R³M² may besuccessfully added to the imine in the absence the complexing reagent.Ancillary ligands that possess chirality may be important in certainolefin polymerization reactions, particularly those that lead to astereospecific polymer, see “Stereospecific Olefin Polymerization withChiral Metallocene Catalysts”, Brintzinger, et al., Angew. Chem. Int.Ed. Engl., 1995, Vol. 34, pp. 1143-1170, and the references therein;Bercaw et al., J. Am. Chem. Soc., 1999, Vol. 121, 564-573; and Bercaw etal., J. Am. Chem. Soc., 1996, Vol. 118, 11988-11989.

Compositions

Once the desired ligand is formed, it may be combined with a metal atom,ion, compound or other metal precursor compound. In some applications,the ligands will be combined with a metal compound or precursor and theproduct of such combination is not determined, if a product forms. Forexample, the ligand may be added to a reaction vessel at the same timeas the metal or metal precursor compound along with the reactants,activators, scavengers, etc. Additionally, the ligand can be modifiedprior to addition to or after the addition of the metal precursor, e.g.through a deprotonation reaction or some other modification.

For formulas I, II, III, IV and V, the metal precursor compounds may becharacterized by the general formula Hf(L)_(n) where L is independentlyselected from the group consisting of halide (F, Cl, Br, I), alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl,substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene,seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates,oxalates, carbonates, nitrates, sulphates, and combinations thereof. nis 1, 2, 3, 4, 5, or 6. The hafnium precursors may be monomeric, dimericor higher orders thereof. It is well known that hafnium metal typicallycontains some amount of impurity of zirconium. Thus, this invention usesas pure hafnium as is commercially reasonable. Specific examples ofsuitable hafnium precursors include, but are not limited to HfCl₄,Hf(CH₂Ph)₄, Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂. Lewis base adducts of theseexamples are also suitable as hafnium precursors, for example, ethers,amines, thioethers, phosphines and the like are suitable as Lewis bases.

For formulas IV and V, the metal precursor compounds may becharacterized by the general formula M(L)_(n) where M is hafnium orzirconium and each L is independently selected from the group consistingof halide (F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates, and combinations thereof. n is 4, typically. It iswell known that hafnium metal typically contains some amount of impurityof zirconium. Thus, this practice uses as pure hafnium or zirconium asis commercially reasonable. Specific examples of suitable hafnium andzirconium precursors include, but are not limited to HfCl₄, Hf(CH₂Ph)₄,Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Cl₂; ZrCl₄, Zr(CH₂Ph)₄,Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)₄, Zr(CH₂Ph)₃Cl, Zr(CH₂CMe₃)₃Cl,Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂, Zr(CH₂CMe₃)₂Cl₂, Zr(CH₂SiMe₃)₂Cl₂,Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMe₂)₂Cl₂, Zr(NEt₂)₂Cl₂, and Zr(N(SiMe₃)₂)₂Cl₂.Lewis base adducts of these examples are also suitable as hafniumprecursors, for example, ethers, amines, thioethers, phosphines and thelike are suitable as Lewis bases.

The ligand to metal precursor compound ratio is typically in the rangeof about 0.01:1 to about 100:1, more preferably in the range of about0.1:1 to about 10:1.

Metal-Ligand Complexes

Generally, the ligand is mixed with a suitable metal precursor compoundprior to or simultaneously with allowing the mixture to be contactedwith the reactants (e.g., monomers). When the ligand is mixed with themetal precursor compound, a metal-ligand complex may be formed, whichmay be a catalyst or may need to be activated to be a catalyst. Themetal-ligand complexes discussed herein are referred to as 2,1 complexesor 3,2 complexes, with the first number representing the number ofcoordinating atoms and second number representing the charge occupied onthe metal. The 2,1-complexes therefore have two coordinating atoms and asingle anionic charge. Other embodiments are those complexes that have ageneral 3,2 coordination scheme to a metal center, with 3,2 referring toa ligand that occupies three coordination sites on the metal and two ofthose sites being anionic and the remaining site being a neutral Lewisbase type coordination.

Looking first at the 2,1-nonmetallocene metal-ligand complexes, themetal-ligand complexes may be characterized by the following generalformula:

wherein T, J″, R¹, L and n are as defined previously; and x is 1 or 2.The J″ heteroaryl may or may not datively bond, but is drawn as bonding.More specifically, the nonmetallocene-ligand complexes may becharacterized by the formula:

wherein R¹, T, R⁴, R⁵, R⁶, R⁷, L and n are as defined previously; and xis 1 or 2. In one preferred embodiment x=1 and n=3. Additionally, Lewisbase adducts of these metal-ligand complexes can also be used, forexample, ethers, amines, thioethers, phosphines and the like aresuitable as Lewis bases.

More specifically, the nonmetallocene metal-ligand complexes may becharacterized by the general formula:

wherein the variables are generally defined above. Thus, e.g., Q², Q³,Q⁴, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heteroalkyl, substituted heteroalkyl,heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl,phosphino, amino, thio, seleno, nitro, and combinations thereof;optionally, two or more R⁴, R⁵, R⁶, R⁷ groups may be joined to form afused ring system having from 3-50 non-hydrogen atoms in addition to thepyridine ring, e.g. generating a quinoline group; also, optionally, anycombination of R², R³ and R⁴ may be joined together in a ring structure;Q¹ and Q⁵ are selected from the group consisting of alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl,provided that Q¹ and Q⁵ are not both methyl; and each L is independentlyselected from the group consisting of halide, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkylheterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl,silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino,phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates,nitrates, sulphates and combinations thereof; n is 1, 2, 3, 4, 5, or 6;and x=1 or 2.

In other embodiments, the 2,1 metal-ligand complexes can becharacterized by the general formula:

wherein the variables are generally defined above.

In still other embodiments, the 2,1 metal-ligand complexes can becharacterized by the general formula:

wherein the variables are generally defined above.

The more specific embodiments of the nonmetallocene metal-ligandcomplexes of formulas VI, VII, VIII, IX and X are explained above withregard to the specifics described for the ligands and metal precursors.Specific examples of 2,1 metal-ligand complexes include, but are notlimited to:

where L, n and x are defined as above (e.g., x=1 or 2) and Ph=phenyl. Inpreferred embodiments, x=1 and n=3. Furthermore in preferredembodiments, L is selected from the group consisting of alkyl,substituted alkyl, aryl, substituted aryl or amino.

Turning to the 3,2 metal-ligand nonmetallocene complexes, themetal-ligand complexes may be characterized by the general formula:

where M is zirconium or hafnium;

R¹ and T are defined above;

J′″ being selected from the group of substituted heteroaryls with 2atoms bonded to the metal M, at least one of those 2 atoms being aheteroatom, and with one atom of J′″ is bonded to M via a dative bond,the other through a covalent bond; and

L¹ and L² are independently selected from the group consisting ofhalide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine,hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio,1,3-dionates, oxalates, carbonates, nitrates, sulphates, andcombinations thereof.

More specifically, the 3,2 metal-ligand nonmetallocene complexes may becharacterized by the general formula:

where M is zirconium or hafnium;

T, R¹, R⁴, R⁵, R⁶, L¹ and L² are defined above; and

E″ is either carbon or nitrogen and is part of an cyclic aryl,substituted aryl, heteroaryl, or substituted heteroaryl group.

Even more specifically, the 3,2 metal-ligand nonmetallocene complexesmay be characterized by the general formula:

where M is zirconium or hafnium; and

T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, L¹ and L² are defined above.

Still even more specifically, the 3,2 metal-ligand nonmetallocenecomplexes may be characterized by the general formula:

where M is zirconium or hafnium; and

T, R¹R⁴, R⁵R⁶, R¹⁰, R¹¹, R¹², R¹³, Q¹, Q², Q³, Q⁴, Q⁵, L¹ and L² aredefined above.

The more specific embodiments of the metal-ligand complexes of formulasXI, XII, XIII and XIV are explained above with regard to the specificsdescribed for the ligands and metal precursors.

In the above formulas, R¹⁰, R¹¹, R¹² and R¹³ are independently selectedfrom the group consisting of hydrogen, halo, alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heteroalkyl, substitutedheteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl,substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy,silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinationsthereof; optionally, two or more R¹⁰, R¹¹, R¹² and R¹³ groups may bejoined to form a fused ring system having from 3-50 non-hydrogen atoms.

In addition, Lewis base adducts of the metal-ligand complexes in theabove formulas are also suitable, for example, ethers, amines,thioethers, phosphines and the like are suitable as Lewis bases.

The metal-ligand complexes can be formed by techniques known to those ofskill in the art. In some embodiments, R¹⁴ is hydrogen and themetal-ligand complexes are formed by a metallation reaction (in situ ornot) as shown below in scheme 3:

In scheme 3, R¹⁴ is hydrogen (but see above for the full definition ofR¹⁴ in other embodiments). The metallation reaction to convert the2,1-complex on the left to the 3,2 complex on the right can occur via anumber of mechanisms, likely depending on the substituents chosen forL¹, L² and L³ and the other substituents such as Q¹-Q⁵, R²-R⁶, R¹⁰ toR¹³. In one embodiment, when L¹, L² and L³ are each N(CH₃)₂, thereaction can proceed by heating the 2,1 complex to a temperature aboveabout 100° C. In this embodiment, it is believed that L¹ and L² remainN(CH₃)₂ in the 3,2 complex. In another embodiment where L¹, L² and L³are each N(CH₃)₂, the reaction can proceed by adding a group 13 reagent(as described below) to the 2,1 complex at a suitable temperature (suchas room temperature). Preferably the group 13 reagent for this purposeis di-isobutyl aluminum hydride, tri-isobutyl aluminum or trimethylaluminum. In this embodiment, L¹ and L² are typically converted to theligand (e.g., alkyl or hydride) stemming from the group 13 reagent(e.g., from trimethyl aluminum, L¹ and L² are each CH₃ in the 3,2complex). The 2,1 complex in scheme 3 is formed by the methods discussedabove.

In an alternative embodiment possibly outside the scope of scheme 3, forisotactic polypropylene production, it is currently preferred that R¹⁴is either hydrogen or methyl.

Specific examples of 3,2 complexes include:

Various references disclose metal complexes that may appear to besimilar; see for example, U.S. Pat. Nos. 6,103,657 and 5,637,660.However, certain embodiments herein provide unexpectedly improvedpolymerization performance (e.g., higher activity and/or higherpolymerization temperatures and/or higher comonomer incorporation and/orcrystalline polymers resulting from a high degree of stereoselectivityduring polymerization) relative to the embodiments disclosed in thosereferences. In particular, as shown in certain of the examples herein,the activity of the hafnium metal catalysts is far superior to that ofthe zirconium catalysts.

The ligands, complexes or catalysts may be supported on an organic orinorganic support. Suitable supports include silicas, aluminas, clays,zeolites, magnesium chloride, polyethylene glycols, polystyrenes,polyesters, polyamides, peptides and the like. Polymeric supports may becross-linked or not. Similarly, the ligands, complexes or catalysts maybe supported on similar supports known to those of skill in the art. Inaddition, the catalysts may be combined with other catalysts in a singlereactor and/or employed in a series of reactors (parallel or serial) inorder to form blends of polymer products. Supported catalysts typicallyproduce P/E*copolymers with an MWD larger than those produce fromunsupported catalysts, although these MWDs are typically less about 6,preferably less than about 5 and more preferably less than about 4.

The metal complexes are rendered catalytically active by combinationwith an activating cocatalyst or by use of an activating technique.Suitable activating cocatalysts include neutral Lewis acids such asalumoxane (modified and unmodified), C₁₋₃₀ hydrocarbyl substituted Group13 compounds, especially tri(hydrocarbyl)aluminum- ortri(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more especiallyperfluorinated tri(aryl)boron compounds, and most especiallytris(pentafluorophenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium salts of compatible,noncoordinating anions; bulk electrolysis (explained in more detailhereinafter); and combinations of the foregoing activating cocatalystsand techniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes in the following references: U.S. Pat. Nos. 5,153,157,5,064,802, 5,721,185 and 5,350,723, and EP-A-277,003 and -A-468,651(equivalent to U.S. Pat. No. 5,321,106).

The alumoxane used as an activating cocatalyst is of the formula (R⁴_(x)(CH₃)_(y)AlO)_(n), in which R⁴ is a linear, branched or cyclic C₁ toC₆ hydrocarbyl, x is from 0 to about 1, y is from about 1 to 0, and n isan integer from about 3 to about 25, inclusive. The preferred alumoxanecomponents, referred to as modified methylaluminoxanes, are thosewherein R⁴ is a linear, branched or cyclic C₃ to C₉ hydrocarbyl, x isfrom about 0.15 to about 0.50, y is from about 0.85 to about 0.5 and nis an integer between 4 and 20, inclusive; still more preferably, R⁴ isisobutyl, tertiary butyl or n-octyl, x is from about 0.2 to about 0.4, yis from about 0.8 to about 0.6 and n is an integer between 4 and 15,inclusive. Mixtures of the above alumoxanes may also be employed.

Most preferably, the alumoxane is of the formula (R⁴_(x)(CH₃)_(y)AlO)_(n), wherein R⁴ is isobutyl or tertiary butyl, x isabout 0.25, y is about 0.75 and n is from about 6 to about 8.

Particularly preferred alumoxanes are so-called modified alumoxanes,preferably modified methylalumoxanes (MMAO), that are completely solublein alkane solvents, for example heptane, and may include very little, ifany, trialkylaluminum. A technique for preparing such modifiedalumoxanes is disclosed in U.S. Pat. No. 5,041,584. Alumoxanes useful asan activating cocatalyst may also be made as disclosed in U.S. Pat. Nos.4,542,199; 4,544,762; 4,960,878; 5,015,749; 5,041,583 and 5,041,585.Various alumoxanes can be obtained from commercial sources, for example,Akzo-Nobel Corporation, and include MMAO-3A, MMAO-12, and PMAO-IP.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to10 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, and combinations of neutral Lewis acids,especially tris(pentafluorophenyl)borane, with nonpolymeric, compatiblenoncoordinating ion-forming compounds are also useful activatingcocatalysts.

Suitable ion forming compounds useful as cocatalysts comprise a cationwhich is a Bronsted acid capable of donating a proton, and a compatible,noncoordinating anion, A⁻. As used herein, the term “noncoordinating”means an anion or substance which either does not coordinate to theGroup 4 metal containing precursor complex and the catalytic derivativederived therefrom, or which is only weakly coordinated to such complexesthereby remaining sufficiently labile to be displaced by a neutral Lewisbase. A noncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

In one embodiment, the activating cocatalysts may be represented by thefollowing general formula:[L*−H]⁺ _(d)[A^(d−)]wherein:

L* is a neutral Lewis base;

[L*−H]⁺ is a Bronsted acid;

A^(d−) is a noncoordinating, compatible anion having a charge of d⁻, and

d is an integer from 1 to 3.

More preferably A^(d−) corresponds to the formula: [M′^(k+)Q_(n)′]^(d−)wherein:

k is an integer from 1 to 3;

n′ is an integer from 2 to 6;

n′−k=d;

M′ is an element selected from Group 13 of the Periodic Table of theElements; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, hydrocarbyl, hydrocarbyloxy, halosubstituted-hydrocarbyl,halosubstituted hydrocarbyloxy, and halo substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, i.e., the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of the catalystsmay be represented by the following general formula:[L*−H]⁺[BQ₄]⁻wherein:

[L*−H]⁺ is as previously defined;

B is boron in an oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy- or fluorinated silylhydrocarbyl-group of upto 20 nonhydrogen atoms, with the proviso that in not more than oneoccasion is Q hydrocarbyl. Most preferably, Q is each occurrence afluorinated aryl group, especially, a pentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the catalysts aretri-substituted ammonium salts such as:

-   -   triethylammonium tetraphenylborate,    -   N,N-dimethylanilinium tetraphenylborate,    -   tripropylammonium tetrakis(pentafluorophenyl) borate,    -   N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,    -   triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,    -   N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate,        and    -   N,N-dimethyl-2,4,6-trimethylanilinium        tetrakis(2,3,4,6-tetrafluorophenyl) borate;

dialkyl ammonium salts such as:

-   -   di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and    -   dicyclohexylammonium tetrakis(pentafluorophenyl) borate;    -   tri-substituted phosphonium salts such as:    -   triphenylphosphonium tetrakis(pentafluorophenyl) borate,    -   tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and    -   tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)        borate;

di-substituted oxonium salts such as:

-   -   diphenyloxonium tetrakis(pentafluorophenyl) borate,    -   di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and    -   di(2,6-dimethylphenyl)oxonium tetrakis(pentafluorophenyl)        borate;

di-substituted sulfonium salts such as:

-   -   diphenylsulfonium tetrakis(pentafluorophenyl) borate,    -   di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and    -   di(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)        borate.        Preferred [L*−H]⁺ cations are N,N-dimethylanilinium and        tributylammonium.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Ox^(e+))_(d)(A^(d−))_(e)wherein:

Ox^(e+) is a cationic oxidizing agent having a charge of e⁺;

e is an integer from 1 to 3; and

A^(d−) and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:©⁺A⁻wherein:

©⁺ is a C₁₋₂₀ carbenium ion; and

A⁻ is as previously defined.

A preferred carbenium ion is the trityl cation, i.e.,triphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:R₃Si(X′)_(q) ⁺A⁻wherein:

R is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakis(pentafluorophenyl)borate,triethylsilylium(tetrakispentafluoro)phenylborate and ether substitutedadducts thereof. Silylium salts have been previously genericallydisclosed in J. Chem Soc. Chem. Comm., 1993, 383-384, as well asLambert, J. B., et al., Organometallics, 1994, 13, 2430-2443.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

The metal complexes can also be activated by technique of bulkelectrolysis which involves the electrochemical oxidation of the metalcomplex under electrolysis conditions in the presence of a supportingelectrolyte comprising a noncoordinating, inert anion. A furtherdiscovered electrochemical technique for generation of activatingcocatalysts is the electrolysis of a disilane compound in the presenceof a source of a noncoordinating compatible anion. This technique ismore fully disclosed and claimed in U.S. Pat. No. 5,625,087.

The foregoing activating techniques and ion forming cocatalysts are alsopreferably used in combination with a tri(hydrocarbyl)aluminum ortri(hydrocarbyl)borane compound having from 1 to 4 carbons in eachhydrocarbyl group.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:100 to 1:1. In one embodiment the cocatalyst can be used incombination with a tri(hydrocarbyl)aluminum compound having from 1 to 10carbons in each hydrocarbyl group. Mixtures of activating cocatalystsmay also be employed. It is possible to employ these aluminum compoundsfor their beneficial ability to scavenge impurities such as oxygen,water, and aldehydes from the polymerization mixture. Preferred aluminumcompounds include trialkyl aluminum compounds having from 1 to 6 carbonsin each alkyl group, especially those wherein the alkyl groups aremethyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentylor isopentyl. The molar ratio of metal complex to aluminum compound ispreferably from 1:10,000 to 100:1, more preferably from 1:1000 to 10:1,most preferably from 1:500 to 1:1. A most preferred borane activatingcocatalyst comprises a strong Lewis acid, especiallytris(pentafluorophenyl)borane.

In some embodiments, two or more different catalysts, including the useof mixed catalysts can be employed. In addition to a nonmetallocene,metal-centered, heteroaryl ligand catalyst, when a plurality ofcatalysts are used, any catalyst which is capable of copolymerizing oneor more olefin monomers to make an interpolymer or homopolymer may beused in embodiments of the invention in conjunction with anonmetallocene, metal-centered, heteroaryl ligand catalyst. For certainembodiments, additional selection criteria, such as molecular weightcapability and/or comonomer incorporation capability, preferably shouldbe satisfied. Two or more nonmetallocene, metal-centered, heteroarylligand catalysts having different substituents can be used in thepractice of certain of the embodiments disclosed herein. Suitablecatalysts which may be used in conjunction with the nonmetallocene,metal-centered, heteroaryl ligand catalysts disclosed herein include,but are not limited to, Ziegler-Natta, metallocene and constrainedgeometry catalysts and variations on one or more of these. They includeany known and presently unknown catalysts for olefin polymerization. Itshould be understood that the term “catalyst” as used herein refers to ametal-containing compound which is used, along with an activatingcocatalyst, to form a catalyst system. The catalyst, as used herein, isusually catalytically inactive in the absence of a cocatalyst or otheractivating technique. However, not all suitable catalysts arecatalytically inactive without a cocatalyst.

One suitable class of catalysts is the constrained geometry catalystsdisclosed in U.S. Pat. Nos. 5,064,802, 5,132,380, 5,703,187 and6,034,021; EP 0 468 651 and 0 514 828; and WO 93/19104 and 95/00526.Another suitable class of catalysts is the metallocene catalystsdisclosed in U.S. Pat. Nos. 5,044,438, 5,057,475, 5,096,867 and5,324,800. The constrained geometry catalysts may be considered asmetallocene catalysts, and both are sometimes referred to in the art assingle-site catalysts.

Another suitable class of catalysts is substituted indenyl containingmetal complexes as disclosed in U.S. Pat. Nos. 5,965,756 and 6,015,868.Other catalysts are disclosed in U.S. Pat. Nos. 6,268,444; 6,515,155;6,613,9210 and in US Patent Application Publication Numbers 2003/0004286and 2002/0165329 and in copending application U.S. Ser. No. 60/393,862.These catalysts tend to have the capability of producing highermolecular weight polymers. Yet other catalysts, cocatalysts, catalystsystems, and activating techniques which may be used include thosedisclosed in WO 96/23010, 99/14250, 98/41529 and 97/42241; Scollard, etal., in J. Am. Chem. Soc 1996, 118, 10008-10009; EP 0 468 537 B1; WO97/22635; EP 0 949 278 A2, 0 949 279 A2, and 1 063 244 A2; U.S. Pat.Nos. 5,408,017, 5,767,208 and 5,907,021; WO 88/05792, 88/05793 and93/25590; U.S. Pat. Nos. 5,599,761 and 5,218,071; WO 90/07526; U.S. Pat.Nos. 5,972,822, 6,074,977, 6,013,819, 5,296,433, 4,874,880, 5,198,401,5,621,127, 5,703,257, 5,728,855, 5,731,253, 5,710,224, 5,883,204,5,504,049, 5,962,714, 5,965,677 and 5,427,991; WO 93/21238, 94/03506,93/21242, 94/00500, 96/00244 and 98/50392; Wang, et al., Organometallics1998, 17, 3149-3151; Younkin, et al., Science 2000, 287, 460-462; Chenand Marks, Chem. Rev. 2000, 100, 1391-1434; Alt and Koppl, Chem. Rev.2000, 100, 1205-1221; Resconi, et al., Chem. Rev. 2000, 100, 1253-1345;Ittel, et al., ChemRev. 2000, 100, 1169-1203; Coates, Chem. Rev., 2000,100, 1223-1251; U.S. Pat. Nos. 5,093,415, 6,303,719 and 5,874,505; andWO 96/13530. Also useful are those catalysts, cocatalysts and catalystsystems disclosed in U.S. Pat. Nos. 6,268,444; 6,515,155; 5,965,756 and6,150,297.

Process Descriptions

The polymers, including the P* and P/E* polymers, used in the practiceof this invention can be made by any convenient process. In oneembodiment, the process reagents, i.e., (i) propylene, (ii) ethyleneand/or one or more unsaturated comonomers, (iii) catalyst, and, (iv)optionally, solvent and/or a molecular weight regulator (e.g.,hydrogen), are fed to a single reaction vessel of any suitable design,e.g., stirred tank, loop, fluidized-bed, etc. The process reagents arecontacted within the reaction vessel under appropriate conditions (e.g.,solution, slurry, gas phase, suspension, high pressure) to form thedesired polymer, and then the output of the reactor is recovered forpost-reaction processing. All of the output from the reactor can berecovered at one time (as in the case of a single pass or batchreactor), or it can be recovered in the form of a bleed stream whichforms only a part, typically a minor part, of the reaction mass (as inthe case of a continuous process reactor in which an output stream isbled from the reactor at the same rate at which reagents are added tomaintain the polymerization at steady-state conditions). “Reaction mass”means the contents within a reactor, typically during or subsequent topolymerization. The reaction mass includes reactants, solvent (if any),catalyst, and products and by-products. The recovered solvent andunreacted monomers can be recycled back to the reaction vessel.

The polymerization conditions at which the reactor is operated aresimilar to those for the polymerization of propylene using a known,conventional Ziegler-Natta catalyst. Typically, solution polymerizationof propylene is performed at a polymerization temperature between about−50 to about 200, preferably between about −10 and about 150, C, andmore preferably between about 20 to about 150C and most preferablybetween about 80 and 150C, and the polymerization pressure is typicallybetween about atmospheric to about 7, preferably between about 0.2 andabout 5, Mpa. If hydrogen is present, then it is usually present at apartial pressure (as measured in the gas phase portion of thepolymerization) of about 0.1 kPa to about 5 Mpa, preferably betweenabout 1 kPa to about 3 Mpa. Gas phase, suspension and otherpolymerization schemes will use conditions conventional for thoseschemes. For gas-phase or slurry-phase polymerization processes, it isdesirable to perform the polymerization at a temperature below themelting point of the polymer.

For the propylene/ethylene copolymer processes described herein,optionally containing additional unsaturated monomer, the weight ratioof propylene to ethylene in the feed to the reactors is preferably inthe range of 10,000:1 to 1;10, more preferably 1,000:1 to 1:1, stillmore preferably 500:1 to 3:1. For the propylene/C₄₋₂₀ α-olefin copolymerprocesses, the weight ratio of propylene to C₄₋₂₀ α-olefin in the feedpreferably is in the range of 10,000:1 to 1:20, more preferably 1,000:1to 1:1, still more preferably 1,000:1 to 3:1.

The post-reactor processing of the recover reaction mass from thepolymerization vessel typically includes the deactivation of thecatalyst, removal of catalyst residue, drying of the product, and thelike. The recovered polymer is then ready for storage and/or use.

The P* and P/E*polymers produced in a single reaction vessel will havethe desired MFR, narrow MWD, ¹³C NMR peaks at 14.6 and 15.7 ppm (thepeaks of approximately equal intensity), high B-value (if a P/E*copolymer), and its other defining characteristics. If, however, abroader MWD is desired, e.g., a MWD of between about 2.5 and about 3.5or even higher, without any substantial change to the other definingcharacteristics of the propylene copolymer, then the copolymer ispreferably made in a multiple reactor system. In multiple reactorsystems, MWD as broad as 15, more preferably 10, most preferably 4-8,can be prepared.

Preferably, to obtain a broad MWD, at least two of the catalysts used ina single reactor have a high weight-average molecular weight(M_(wH))/low weight average molecular weight (M_(wL)) ratio(M_(wH)/M_(wL), as defined later) in the range from about 1.5 to about10, and the process used is a gas phase, slurry, or solution process.More preferably, at least two of the catalysts used in a single reactorhave M_(wH)/M_(wL) in the range from about 1.5 to about 10, and theprocess used is a continuous solution process, especially a continuoussolution process wherein the polymer concentration in the reactor atsteady state is at least 15% by weight of the reactor contents. Stillmore preferably, at least two of the catalysts used in a single reactorhave M_(wH)/M_(wL) in the range from about 1.5 to about 10, and theprocess used is a continuous solution process wherein the polymerconcentration in the reactor at steady state is at least 18% by weightof the reactor contents. Most preferably, at least two of the catalystsused in a single reactor have M_(wH)/M_(wL) in the range from about 1.5to about 10, and the process used is a continuous solution processwherein the polymer concentration in the reactor at steady state is atleast 20% by weight of the reactor contents.

In one embodiment, the monomers comprise propylene and at least oneolefin selected from the group consisting of C₄-C₁₀ α-olefins,especially 1-butene, 1-hexene, and 1-octene, and the melt flow rate(MFR) of the interpolymer is preferably in the range of about 0.1 toabout 500, more preferably in the range from about 0.1 to about 100,further more preferably about 0.2 to 80, most preferably in the range of0.3-50. In some embodiments, the nonmetallocene, catalysts describedherein may be utilized in combination with at least one additionalhomogeneous or heterogeneous polymerization catalyst in separatereactors connected in series or in parallel to prepare polymer blendshaving desirable properties. An example of such a process is disclosedin WO 94/00500, equivalent to U.S. Ser. No. 07/904,770, as well as U.S.Pat. Nos. 5,844,045; 5,869,575 and 6,448,341. Included in theseembodiments is the use of two different nonmetallocene, metal-centered,heteroaryl ligand catalysts.

The catalyst system may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent in whichpolymerization will be carried out by solution polymerizationprocedures. The catalyst system may also be prepared and employed as aheterogeneous catalyst by adsorbing the requisite components on acatalyst support material such as silica gel, alumina or other suitableinorganic support material. When prepared in heterogeneous or supportedform, it is preferred to use silica as the support material. Theheterogeneous form of the catalyst system may be employed in a slurry orgas phase polymerization. As a practical limitation, slurrypolymerization takes place in liquid diluents in which the polymerproduct is substantially insoluble. Preferably, the diluent for slurrypolymerization is one or more hydrocarbons with less than 5 carbonatoms. If desired, saturated hydrocarbons such as ethane, propane orbutane may be used in whole or part as the diluent. Likewise theα-olefin comonomer or a mixture of different α-olefin comonomers may beused in whole or part as the diluent. Most preferably, the major part ofthe diluent comprises at least the α-olefin monomer or monomers to bepolymerized.

Solution polymerization conditions utilize a solvent for the respectivecomponents of the reaction. Preferred solvents include, but are notlimited to, mineral oils and the various hydrocarbons which are liquidat reaction temperatures and pressures. Illustrative examples of usefulsolvents include, but are not limited to, alkanes such as pentane,iso-pentane, hexane, heptane, octane and nonane, as well as mixtures ofalkanes including kerosene and Isopar E™, available from Exxon ChemicalsInc.; cycloalkanes such as cyclopentane, cyclohexane, andmethylcyclohexane; and aromatics such as benzene, toluene, xylenes,ethylbenzene and diethylbenzene.

The polymerization may be carried out as a batch or a continuouspolymerization process. A continuous process is preferred, in whichevent catalysts, solvent or diluent (if employed), and comonomers (ormonomer) are continuously supplied to the reaction zone and polymerproduct continuously removed therefrom. The polymerization conditionsfor manufacturing the interpolymers are generally those useful in thesolution polymerization process, although the application is not limitedthereto. Gas phase and slurry polymerization processes are also believedto be useful, provided the proper catalysts and polymerizationconditions are employed.

The following procedure may be carried out to obtain a P/E* copolymer.In a stirred-tank reactor propylene monomer is introduced continuouslytogether with solvent, and ethylene monomer. The reactor contains aliquid phase composed substantially of ethylene and propylene monomerstogether with any solvent or additional diluent. If desired, a smallamount of a “H”-branch inducing diene such as norbornadiene,1,7-octadiene or 1,9-decadiene may also be added. A nonmetallocene,metal-centered, heteroaryl ligand catalyst and suitable cocatalyst arecontinuously introduced in the reactor liquid phase. The reactortemperature and pressure may be controlled by adjusting thesolvent/monomer ratio, the catalyst addition rate, as well as by coolingor heating coils, jackets or both. The polymerization rate is controlledby the rate of catalyst addition. The ethylene content of the polymerproduct is determined by the ratio of ethylene to propylene in thereactor, which is controlled by manipulating the respective feed ratesof these components to the reactor. The polymer product molecular weightis controlled, optionally, by controlling other polymerization variablessuch as the temperature, monomer concentration, or by a stream ofhydrogen introduced to the reactor, as is known in the art. The reactoreffluent is contacted with a catalyst kill agent, such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off unreacted gaseous ethylene and propylene aswell as residual solvent or diluent at reduced pressure, and, ifnecessary, conducting further devolatilization in equipment such as adevolatilizing extruder or other devolatilizing equipment operated atreduced pressure. For a solution polymerization process, especially acontinuous solution polymerization, preferred ranges of propyleneconcentration at steady state are from about 0.05 weight percent of thetotal reactor contents to about 50 weight percent of the total reactorcontents, more preferably from about 0.5 weight percent of the totalreactor contents to about 30 weight percent of the total reactorcontents, and most preferably from about 1 weight percent of the totalreactor contents to about 25 weight percent of the total reactorcontents. The preferred range of polymer concentration (otherwise knownas % solids) is from about 3% of the reactor contents by weight to about45% of the reactor contents or higher, more preferably from about 10% ofthe reactor contents to about 40% of the reactor contents, and mostpreferably from about 15% of the reactor contents to about 40% of thereactor contents.

In a continuous process, the mean residence time of the catalyst andpolymer in the reactor generally is from 5 minutes to 8 hours, andpreferably from 10 minutes to 6 hours, more preferably from 10 minutesto 1 hour.

In some embodiments, ethylene is added to the reaction vessel in anamount to maintain a differential pressure in excess of the combinedvapor pressure of the propylene and diene monomers. The ethylene contentof the polymer is determined by the ratio of ethylene differentialpressure to the total reactor pressure. Generally the polymerizationprocess is carried out with a pressure of ethylene of from 10 to 1000psi (70 to 7000 kPa), most preferably from 40 to 800 psi (30 to 600kPa). The polymerization is generally conducted at a temperature of from25 to 250° C., preferably from 75 to 200° C., and most preferably fromgreater than 95 to 200° C.

In another embodiment, a process for producing a propylene homopolymeror interpolymer of propylene with at least one additional olefinicmonomer selected from ethylene or C₄₋₂₀ α-olefins comprises thefollowing steps: 1) providing controlled addition of a nonmetallocene,metal-centered, heteroaryl ligand catalyst to a reactor, including acocatalyst and optionally a scavenger component; 2) continuously feedingpropylene and optionally one or more additional olefinic monomersindependently selected from ethylene or C₄₋₂₀ α-olefins into thereactor, optionally with a solvent or diluent, and optionally with acontrolled amount of H₂; and 3) recovering the polymer product.Preferably, the process is a continuous solution process. Thecocatalysts and optional scavenger components in the novel process canbe independently mixed with the catalyst component before introductioninto the reactor, or they may each independently be fed into the reactorusing separate streams, resulting in “in reactor” activation. Scavengercomponents are known in the art and include, but are not limited to,alkyl aluminum compounds, including alumoxanes. Examples of scavengersinclude, but are not limited to, trimethyl aluminum, triethyl aluminum,triisobutyl aluminum, trioctyl aluminum, methylalumoxane (MAO), andother alumoxanes including, but not limited to, MMAO-3A, MMAO-7, PMAO-IP(all available from Akzo Nobel).

As previously noted, the process described above may optionally use morethan one reactor. The use of a second reactor is especially useful inthose embodiments in which an additional catalyst, especially aZiegler-Natta or chrome catalyst, or a metallocene catalyst, especiallya CGC, is employed. The second reactor typically holds the additionalcatalyst.

By proper selection of process conditions, including catalyst selection,polymers with tailored properties can be produced. For a solutionpolymerization process, especially a continuous solution polymerization,preferred ranges of ethylene concentration at steady state are from lessthan about 0.02 weight percent of the total reactor contents to about 5weight percent of the total reactor contents, and the preferred range ofpolymer concentration is from about 10% of the reactor contents byweight to about 45% of the reactor contents or higher.

In general, catalyst efficiency (expressed in terms of gram of polymerproduced per gram of transition metal) decreases with increasingtemperature and decreasing ethylene concentration. In addition, themolecular weight of the polymer product generally decreases withincreasing reactor temperature and decreases with decreasing propyleneand ethylene concentration. The molecular weight of the polyolefin canalso be controlled with the addition of chain transfer compounds,especially through the addition of H₂.

The gas phase processes are continuous processes which provide for thecontinuous supply of reactants to the reaction zone of the reactor andthe removal of products from the reaction zone of the reactor, therebyproviding a steady-state environment on the macro scale in the reactionzone of the reactor. Products are readily recovered by exposure toreduced pressure and optionally elevated temperatures (devolatilization)according to known techniques. Typically, the fluidized bed of the gasphase process is operated at temperatures greater than 50° C.,preferably from about 60° C. to about 110° C., more preferably fromabout 70° C. to about 110° C.

A number of patents and patent applications describe gas phaseprocesses, particularly, U.S. Pat. Nos. 4,588,790; 4,543,399; 5,352,749;5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562;5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019;5,616,661; and EP applications 659,773; 692,500; 780,404; 697,420;628,343; 593,083; 676,421; 683,176; 699,212; 699,213; 721,798; 728,150;728,151; 728,771; 728,772; 735,058; and PCT Applications WO94/29032,WO94/25497, WO94/25495, WO94/28032, WO95/13305, WO94/26793, WO95/07942,WO97/25355, WO93/11171, WO95/13305, and WO95/13306.

Nucleating Agents

Any semi-crystalline polymer that will initiate nucleation in a P* andP/E* polymer can be used as the nucleating agent of this invention. Ashere used, “semi-crystalline polymer” and similar terms mean a polymerwith a crystallinity of at least about 40% as measured by DSC at 10degrees/minute. Typically, the nucleating agent is a semi-crystallinepolyolefin, and preferably it is a semi-crystalline branched or coupledpolyolefin.

Representative branched nucleating agents include semi-crystallinehomopolymers of ethylene, propylene and other α-olefins,semi-crystalline copolymers of ethylene and propylene and/or one or moreC₄₋₂₀ α-olefins or dienes, and semi-crystalline, hetero-branchedcopolymers. These agents can either be inherently branched or branchingcan be induced by any known method, e.g., exposure to e-beam or UVradiation. Hetero-branched copolymers include all possible types ofbranched polymer structures in which the polymer branches, here definedas polymer segments that emanate from a branch point and have one freeend (denoted as “branches”) and/or polymer segments that run between twobranch points (denoted as “segments”) are compositionally different.This compositional difference can be between branches and segments, oramong different branches, or among different segments, or a combinationof these possibilities. Examples of types of branched polymer structuresare tree, comb, graft, star and random. Semi-crystalline refers to thesubclass of hetero-branched copolymers where either the branches orsegments or both are semi-crystalline in whole or part. Preferably thebranches are semi-crystalline in whole or part. Higher crystallinity ofthe branches is preferred.

Representative coupled nucleating agents include coupledsemi-crystalline homopolymers of ethylene, propylene and/or otherα-olefins, and coupled semi-crystalline copolymers of ethylene andpropylene and/or one or more C₄₋₂₀ α-olefins or dienes. These homo-and/or copolymers are coupled together by one or more coupling agents.As here used, a coupling agent is a polyfunctional compound, i.e., acompound comprising two or more functional groups, capable of insertionreactions into C—H bonds under appropriate reaction conditions. Thoseskilled in the art are familiar with C—H insertion reactions andfunctional groups capable of such reactions. For instance, carbenes asgenerated from diazo compounds are cited in Mathur, N. C. et al.,Tetrahedron, (1985), 41(8), pages 1509-1516, and nitrenes as generatedfrom azides are cited in Abramovitch, R. A., et al., J. Org. Chem.,(1977), 42 (17), pages 2920-6. Azide coupling agents are representativeof the coupling agents that can be used to make the coupled nucleatingagents used in the practice of this invention, and these include thealkyl and aryl azides, acyl azides, azidoformates, phosphoryl azides,phosphinic azides, silyl azides and poly(sulfonyl azides). Thenucleating agents used in the practice of this invention can be bothbranched and coupled.

The nucleating agents of this invention are used in the same manner andunder like conditions as known nucleating agents. The agents can beblended with the P* and P/E* polymer to be crystallized eitherin-reactor or post-reactor. In-reactor addition includes the formationof the agent along with the polymer in the same reactor. The agents areused in an amount sufficient to initiate crystallization. Typically, atleast about 0.1, preferably at least about 0.2 and more preferably atleast about 0.5, weight percent agent is used based on the weight of thepolymer to be crystallized. Practical considerations, e.g., cost,efficiency, etc., are the only limits on the maximum amount of agentthat can be used. Typically, the maximum amount of agent used does notexceed about 10, preferably it does not exceed about 7 and morepreferably it does not exceed about 5 weight percent based on the weightof the polymer to be crystallized. If the agent is added to the polymerto be crystallized post-reactor, then the agent is added in anyconvenient manner, e.g., batch (either neat or diluted with a carrier),metered, etc., and under temperature, pressure, mixing, etc. conditionsthat promote intimate admixture.

The P/E* polymers demonstrate a much enhanced crystalline nucleation inthe presence of a nucleating agent, e.g., a branched polypropylenehomopolymer, than does a comparable P/E polymer, e.g., a polymer alikein essentially all material aspects to the P/E* polymer except that itwas prepared by a metallocene catalyst as opposed to a nonmetallocene,metal-centered heteroaryl ligand catalyst. This enhancement can beexpressed by the ratio (“r”) of the difference between the Tc (i.e., thetemperature in degrees C. of the onset of crystallization) of the P/E*polymer in combination with the nucleating agent and the P/E* polymerneat, and the difference between the Tc of the P/E polymer incombination with the nucleating agent and the P/E polymer neat. The Tcis measured for all under the same conditions, the P/E polymer iscomparable to the P/E* polymer, and the blends are alike is all materialaspects except that one contains P/E polymer and the other contains P/E*polymer. This can be expressed as:r=(Tc P/E*blend)−(Tc P/E*neat)/(Tc P/E blend)−(Tc P/E neat)Preferably, sufficient nucleating agent is blended with the P/E* polymersuch that r is at least about 1.0, more preferably at least about 1.2and even more preferably at least about 1.5. Practical considerationsare the only limitations on the maximum value of r. These r values areof particular interest with respect to P/E* polymers containing betweenabout 3 and 18 weight percent ethylene, and the nucleating agent is asemi-crystalline polyolefin, particularly a semi-crystalline branched orcoupled polypropylene homopolymer.

The greater the Tc, usually the more desirable the polymer for certainapplications, e.g., extrusion and molding applications, fibermanufacture, etc. Generally, nucleated propylene polymers that have ahigher Tc as compared to some other nucleated or unnucleated propylenepolymer will exhibit a shorter cycle time and thus faster throughputduring processing, and better optics in the final product. Moreover,nucleated propylene polymers with an r value in excess of 1 will showsimilar processing and optics advantages relative to a nucleated polymerwith an r value less than or equal to 1. The greater the r value and/orthe higher the Tc of a particular composition of polymer plus nucleatingagent, then generally the faster will be the crystallization that isexhibited.

The following examples are given to illustrate various embodiments ofthe invention. They do not intend to limit the invention as otherwisedescribed and claimed. All numerical values are approximate. When anumerical range is given, it should be understood that embodimentsoutside the range are still within the scope of the invention unlessotherwise indicated. In the following examples, various polymers werecharacterized by a number of methods. Performance data of these polymerswere also obtained. Most of the methods or tests were performed inaccordance with an ASTM standard, if applicable, or known procedures.All parts and percentages are by weight unless otherwise indicated FIGS.10A-J illustrate the chemical structures of various catalysts describedin the following examples.

SPECIFIC EMBODIMENTS

Tetrahydrofuran (THF), diethyl ether, toluene, hexane, and ISOPAR E(obtainable from Exxon Chemicals) are used following purging with pure,dry nitrogen and passage through double columns charged with activatedalumina and alumina supported mixed metal oxide catalyst (Q-5 catalyst,available from Engelhard Corp). All syntheses and handling of catalystcomponents are performed using rigorously dried and deoxygenatedsolvents under inert atmospheres of nitrogen or argon, using eitherglove box, high vacuum, or Schlenk techniques, unless otherwise noted.MMAO-3A, PMAO, and PMAO-IP can be purchased from Akzo-Nobel Corporation.

Synthesis of (C₅Me₄SiMe₂N^(t)Bu)Ti(η⁴-1,3-pentadiene) (Catalyst A, FIG.10A)

Catalyst A can be synthesized according to Example 17 of U.S. Pat. No.5,556,928.

Synthesis of dimethylsilyl(2-methyl-s-indacenyl)(t-butylamido) titanium1,3-pentadiene (Catalyst B. FIG. 10B)

Catalyst B can be synthesized according to Example 23 of U.S. Pat. No.5,965,756.

Synthesis of(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium(Catalyst C. FIG. 10C) (1) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di(p-tolyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium

(A) Preparation ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine

To a 1.70 g (5.35 mmol) ofN-(tert-butyl)-N-(1-chloro-1,1-di(3-p-tolyl)silylamine dissolved in 20mL of THF is added 1.279 g (5.35 mmol) of1-(1H-3-indenyl)-1-(2,3-dihydro-1H-isoindolinyl) lithium salt dissolvedin 20 mL of THF. After the addition, the reaction mixture is stirred for9 hours and then solvent is removed under reduced pressure. The residueis extracted with 40 mL of hexane and filtered. Solvent is removed underreduced pressure giving 2.806 of product as a gray solid.

¹H (C₆D₆) δ: 1.10 (s, 9H), 2.01 (s, 3H), 2.08 (s, 3H), 4.12 (d, 1H,³J_(H-H)=1.5 Hz), 4.39 (d, 1H, ²J_(H-H)=11.1 Hz), 4.57 (d, 1H,²J_(H-H)=11.7 Hz), 5.55 (d, 1H, ³J_(H-H)=2.1 Hz), 6.9-7.22 (m, 10H),7.56 (d, 1H, ³J_(H-H)=7.8 Hz), 7.62 (d, 1H, ³J_(H-H)=6.9 Hz), 7.67 (d,1H, ³J_(H-H)=7.8 Hz), 7.83 (d, 1H, ³J_(H-H)=7.8 Hz).

¹³C{¹H} (C₆D₆) δ: 21.37, 21.43, 33.78, 41.09, 50.05, 56.56, 104.28,120.98, 122.46, 123.84, 124.71, 124.84, 126.98, 128.29, 128.52, 129.05,132.99, 133.68, 135.08, 135.90, 136.01, 138.89, 139.05, 139.09, 141.27,146.39, 148.48.

(B) Preparation ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine,dilithium salt

To a 50 mL hexane solution containing 2.726 g (5.61 mmol) of theN-(tert-butyl)-N-(1,1-p-tolyl)-1-(3-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amineis added 7.4 mL of 1.6 M n-BuLi solution. During addition of the n-BuLi,a yellow precipitate appears. After stirring for 6 hours, the yellowprecipitate is collected on a frit, washed with 2×25 mL of hexane, anddried under reduced pressure to give 2.262 g of the product as a yellowpowder.

¹H (C₆D₆) δ: 1.17 (s, 9H), 2.30 (s, 6H), 4.51 (s, 4H), 6.21 (s, 1H),6.47 (m, 2H), 6.97 (d, 4H, ³J_(H-H)=8.1 Hz), 7.15 (m, 2H), 7.23 (m, 2H),7.50 (m, 1H), 7.81 (d, 4H, ³J_(H-H)=7.8 Hz), 8.07 (d, 1H, ³J_(H-H)=7.2Hz). ¹³C{¹H} (C₆D₆) δ: 21.65, 38.83, 52.46, 59.82, 95.33, 112.93,114.15, 115.78, 118.29, 122.05, 122.60, 124.16, 124.78, 126.94, 127.30,133.06, 134.75, 137.30, 141.98, 148.17.

(C) Preparation ofdichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titanium

In the drybox 1.552 g (4.19 mmol) of TiCl₃(THF)₃ is suspended in 20 mLof THF. To this solution, 2.206 g (4.19 mmol) ofN-(tert-butyl)-N-(1,1-p-tolyl)-1-(1,3-dihydro-2H-isoindol-2-yl)-1H-indenyl)silyl)amine,dilithium salt dissolved in 30 mL of THF is added within 1 minute. Thesolution is then stirred for 60 minutes. After this time, 0.76 g ofPbCl₂ (2.75 mmol) is added and the solution is stirred for 60 minutes.The THF is then removed under reduced pressure. The residue is firstextracted with 60 mL of methylene chloride and filtered. Solvent isremoved under reduced pressure leaving a black crystalline solid. Hexaneis added (30 mL) and the black suspension is stirred for 10 hour. Thesolids are collected on a frit, washed with 30 mL of hexane and driedunder reduced pressure to give 2.23 g of the desired product as a deeppurple solid.

¹H (THF-d₈) δ: 1.40 (s, 9H), 2.46 (s, 3H), 2.48 (s, 3H), 5.07 (d, 2H,²J_(H-H)=12.3 Hz), 5.45 (d, 2H, ²J_(H-H)=12.6 Hz), 5.93 (s, 1H), 6.95(d, 1H, ³J_(H-H)=9.0 Hz), 7.08 (d, 1H, ³J_(H-H)=7.8 Hz), 7.15-7.4 (m,9H), 7.76 (d, 1H, ³J_(H-H)=7.8 Hz), 7.82 (d, 1H, ³J_(H-H)=7.5 Hz), 8.05(d, 1H, ³J_(H-H)=8.7 Hz). ¹³C{¹H} (THF-d₈) δ: 21.71, 21.76, 33.38,56.87, 61.41, 94.5, 107.95, 122.86, 125.77, 126.68, 127.84, 127.92,128.40, 128.49, 129.36, 129.79, 131.23, 131.29, 135.79, 136.43, 136.73,141.02, 141.22, 150.14.

(2) Preparation of(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)dimethyltitanium

In the drybox 0.50 g ofdichloro(N-(1,1-dimethylethyl)-1,1-di-p-tolyl-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)titaniumcomplex (0.79 mmol) is dissolved in 30 mL of diethyl ether. To thissolution, 1.14 mL (1.6 mmol) of MeLi (1.6 M in ether) is added dropwisewhile stirring over a 1 minute period. After the addition of MeLi iscompleted, the solution is stirred for 1.5 hour. Diethyl ether isremoved under reduced pressure and the residue extracted with 45 mL ofhexane. Hexane is removed under reduced pressure giving a redcrystalline material. This solid is dissolved in about 7 mL of tolueneand 25 mL of hexane, filtered, and the solution was put into the freezer(−27° C.) for 2 days. The solvent is then decanted and the resultingcrystals are washed with cold hexane and dried under reduced pressure togive 156 mg of product.

¹H (C₆D₆) δ: 0.25 (s, 3H), 0.99 (3H), 1.72 (s, 9H), 2.12 (s, 3H), 2.15(s, 3H), 4.53 (d, 2H, ²J_(H-H)=11.7 Hz), 4.83 (d, 2H, ²J_(H-H)=11.7 Hz),5.68 (s, 1H), 6.72 (dd, 1H, ³J_(H-H)=8.6 Hz, ³J_(H-H)=6.6 Hz), 6.9-7.2(m, 11H), 7.30 (d, 1H, ³J_(H-H)=8.6 Hz) 7.71 (d, 1H, ³J_(H-H)=8.5 Hz),7.93 (d, 1H, ³J_(H-H)=7.8 Hz), 8.11 (d, 1H, ³J_(H-H)=7.8 Hz). ¹³C{¹H}(C₆D₆) δ: 21.45, 21.52, 35.30, 50.83, 56.03, 56.66, 57.65, 83.80,105.64, 122.69, 124.51, 124.56, 125.06, 125.35, 127.33, 128.98, 129.06,129.22, 133.51, 134.02, 134.62, 136.49, 136.84, 137.69, 139.72, 139.87,143.84.

Synthesis of (1H-cyclopenta [1]phenanthrene-2-yl)dimethyl(t-butylamido)silane titanium dimethyl(Catalyst D. FIG. 10D)

Catalyst D can be synthesized according to Example 2 of U.S. Pat. No.6,150,297.

Synthesis ofrac-[dimethylsilylbis(1-(2-methyl-4-phenyl)indenyl)]zirconium(1,4-diphenyl-1,3-butadiene) (Catalyst E, FIG. 10E)

Catalyst E can be synthesized according to Example 15 of U.S. Pat. No.5,616,664.

Synthesis of rac-[1,2-ethanediylbis(1-indenyl)]zirconium(1,4-diphenyl-1,3-butadiene) (Catalyst F, FIG. 10F)

Catalyst F can be synthesized according to Example 11 of U.S. Pat. No.5,616,664.

Synthesis of Catalyst G, FIG. 10G

Hafnium tetrakisdimethylamine. The reaction is prepared inside of a drybox. A 500 mL round bottom flask containing a stir bar, is charged with200 mL of toluene and LiNMe₂ (21 g, 95%, 0.39 mol). HfCl₄ (29.9 g, 0.093mol) is added slowly over 2 h. The temperature reaches 55° C. Themixture is stirred overnight at ambient temperature. The LiCl isfiltered off. The toluene is carefully distilled away from the product.Final purification is achieved by distillation with a vacuum transferline attached to a cold (−78° C.) receiving flask. This process isperformed outside the dry box on a Schlenk line. The material isdistilled over at 110-120° C. at 300-600 microns. The 19.2 g of thewhite solid is collected.

2-formyl-6-naphthylpyridine. Inside of a dry box, naphthylboronic acid(9.12 g, 53.0 mmol) and Na₂CO₃ (11.64 g, 110 mmol) are dissolved in 290mL of degassed 4:1H₂O/MeOH. This solution is added to a solution of 8 g(43 mmol) of 2-bromo-6-formylpyridine and 810 mg (0.7 mmol) of Pd(PPh₃)₄in 290 mL of degassed toluene. The charged reactor is removed from thedry box, while under a blanket of N₂ and is connected to the house N₂line. The biphasic solution is vigorously stirred and heated to 70° C.for 4 h. On cooling to RT, the organic phase is separated. The aqueouslayer is washed with 3×75 mL of Et₂O. The combined organic extracts arewashed with 3×100 mL of H₂O and 1×100 mL of brine and dried over Na₂SO₄.After removing the volatiles in vacuo, the resultant light yellow oil ispurified via trituration with hexanes. The isolated material isrecrystallized from a hot hexane solution and ultimately yielded 8.75 g,87% yield. mp 65-66° C.

¹H NMR (CDCl₃) δ 7.2-8.3 (m, 10H), 10.25 (s, 1H) ppm. ¹³C NMR (CDCl₃)120.3, 125.64, 125.8, 126.6, 127.26, 128.23, 129.00, 129.74, 130.00,131.39, 134.42, 137.67, 137.97, 153.07, 160.33, 194.23 ppm.

6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine: A dry, 500 mL 3-neckround bottom flask is charged with a solution of 5.57 g (23.9 mmol) of2-formyl-6-naphthlypyridine and 4.81 g (27.1 mmol) of2,6-diisopropylaniline in 238 mL of anhydrous THF containing 3 Åmolecular sieves (6 g) and 80 mg of p-TsOH. The loading of the reactoris performed under N₂. The reactor is equipped with a condenser, an overhead mechanical stirrer and a thermocouple well. The mixture is heatedto reflux under N₂ for 12 h. After filtration and removal of thevolatile in vacuo, the crude, brown oil is triturated with hexanes. Theproduct is filtered off and rinsed with cold hexanes. The slightly offwhite solid weighs 6.42 g. No further purification is performed. mp142-144° C.

¹H NMR (CDCl₃) δ 1.3 (d, 12H), 3.14 (m, 2H), 7.26 (m, 3H), 7.5-7.6 (m,5H), 7.75-7.8 (m, 3H), 8.02 (m 1H), 8.48 (m, 2H) ppm. ¹³C NMR (CDCl₃)23.96, 28.5, 119.93, 123.50, 124.93, 125.88, 125.94, 126.49, 127.04,127.24, 128.18, 128.94, 129.7, 131.58, 134.5, 137.56, 137.63, 138.34,148.93, 154.83, 159.66, 163.86 ppm.

(6-naphthyl-2-pyridyl)-N-(2,6-diisopropylphenyl)benzylamine: A 250 mL3-neck flask, equipped with mechanical stirrer and a N₂ sparge, ischarged with 6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (6.19 mg,15.8 mmol) and 80 mL of anhydrous, degassed Et₂O. The solution is cooledto −78° C. while a solution of phenyllithium (13.15 mL of 1.8 M incyclohexane, 23.7 mmol) is added dropwise over 10 min. After warming toRT over 1 h. the solution is stirred at RT for 12 hours. The reaction isthen quenched with ˜50 mL of aq. NH₄Cl. The organic layer is separated,washed with brine and H₂O, then dried over Na₂SO₄. Using the BiotageChromatography system (column # FK0-1107-19073, 5% THF/95% hexanes), theproduct is isolated as a colorless oil. The chromatography is performedby dissolving the crude oil in 50 mL of hexanes. The purification isperformed in 2×˜25 mL batches, using half of the hexane stock solutionfor each run. 7.0 g of the oil is isolated (93% yield).

¹H NMR (CDCl₃) δ 0.90 (d, 12H), 3.0 (m, 2H), 4.86 (s, 1H), 5.16 (s, 1H),7.00 (m, 3H), 7.1-7.6 (m, 12H), 7.8-7.88 (m, 2H), 7.91-7.99 (d, 1H) ppm.¹³C NMR (CDCl₃) 24.58, 28.30, 70.02, 121.14, 123.62, 123.76, 123.95,125.71, 126.32, 126.55, 126.74, 127.45, 128.04, 128.74, 129.47, 131.66,134.49, 137.4, 138.95, 142.68, 143.02, 143.89, 159.36, 162.22 ppm.

Catalyst G-(Nme₂)₃: The reaction is performed inside of a dry box. A 100mL round bottom flask is charged with Hf(Nme₂)₄ (2.5 g, 5.33 mmol), 30mL of pentane and a stir bar. The amine 1 is dissolve in 40 mL ofpentane then added to the stirring solution of Hf(Nme₂)₄. The mixture isstirred at ambient temperature for 16 h (overnight). The light yellowsolid is filtered off and rinsed with cold pentane. The dry weight ofthe powder is 2.45 g. A second crop is collected from the filtrateweighing 0.63 g. The overall yield is 74%.

¹H NMR (C₆D₆) δ 0.39 (d, 3H, J=6.77 Hz), 1.36 (d, 3H, J=6.9 Hz), 1.65(d, 3H, J=6.68 Hz), 1.76 (d, 3H, J=6.78 Hz), 2.34 (br s, 6H), 2.80 (brs, 6H), 2.95 (br s, 6H), 3.42 (m, 1H, J=6.8 Hz), 3.78 (m, 1H, J=6.78Hz), 6.06 (s, 1H), 6.78 (m, 2H), 6.94 (m, 1H), 7.1-7.4 (m, 13H), 7.8 (m,2H) ppm.

Catalyst G: The reaction is performed inside of a dry box. A 100 mLround bottom flask is charged with 70 mL of pentane and 15 mL of a 2.0 Mtrimethyl aluminum in hexane solution. The solution is cooled to −40° C.The hafnium trisamide compound from the previous reaction (1.07, g 1.28mmol) is added in small portions over 5-10 minutes. Upon the addition, awhite gelatinous residue forms. After 45-60 min the reaction becomesyellow with a fine, yellow, powder precipitating from the mixture. Aftera total reaction time of 2.5 h the mixture is filtered and 615 mg ofCatalyst G is isolated as a bright, yellow powder. No furtherpurification is performed.

¹H NMR (C₆D₆) δ 0.51 (d, 3H, J=6.73 Hz), 0.79 (s, 3H), 1.07 (s, 3H),1.28 (d, 3H, J=6.73 Hz), 1.53(m, 6H), 3.37 (m, 1H, J=6.75 Hz), 3.96 (m,1H, J=6.73 Hz), 6.05 (s, 1H), 6.50 (d, 1H, J=7.75 Hz), 6.92 (t, 1H,J=7.93 Hz), 7.1-7.59 (m, 12H), 7.6 (d, 1H), 7.8-8.0 (m, 2H), 8.3 (m,1H), 8.69 (d, 1H, J=7.65 Hz) ppm.

Synthesis of Catalyst H, FIG. 10H

To a solution of 9-bromophenanthrene (10.36 mg, 41 mmol) in 132 mL ofanhydrous, degassed Et₂O cooled to −40° C. is added under N₂ 27 mL (43.2mmol) of a 1.6 M solution of n-BuLi in hexanes. The solution is swirledto mix and allowed to react at −40° C. for 3 hours during whichcolorless crystals precipitated from solution. The9-phenanthrenyllithium is added as a slurry to a well-mixed solution of6-naphthylpyridine-2-(2,6-diisopropylphenyl)imine (10.6 g, 27.04 mmol)in 130 mL of Et₂O cooled to −40° C. After warming to ambient temperatureover 1 h, the solution is stirred at ambient temperature for 2 hours.The reaction is then quenched with aq. NH₄Cl, and subjected to anaqueous/organic work-up. The organic washes are combined and dried overNa₂SO₄. Upon removal of the volatiles with rotary evaporation, theproduct precipitates from solution. The isolated solids are rinsed withcold hexanes. The material is vacuum dried at 70° C. using the housevacuum over night. The dried material is isolated as a white solid,weighing 12.3 g for a yield of 80%. A second crop is isolated weighing0.37 g. Mp 166-168° C.

¹H NMR (C₆D₆) δ 1.08 (dd, 12H), 3.43 (m, 2H), 5.47 (m, 1H), 6.16 (d,1H), 7.0-7.8 (m, 14H), 8.2 (d, 1H), 8.5-8.6 (m, 4H), ppm. ¹³C NMR(CDCl₃) 24.68, 28.22, 68.87, 120.56, 122.89, 123.63, 123.73, 124.07,124.1, 125.5, 125.59, 126.24, 126.42, 126.52, 126.76, 126.83, 126.9,127.05, 127.14, 128.0, 128.55, 129.49, 129.55, 130.67, 130.71, 131.52,131.55, 132.24, 134.39, 137.57, 143.31, 159.1, 162 ppm.

Catalyst H-(Nme₂)₃: Inside of a dry box, six different teflon-screwcapped, glass pressure tube reactors are each charged with Hf(Nme₂)₄(1.55 g, 4.37 mmol, overall 9.3 g, 26.2 mmol), 10 mL of toluene and theligand isolated from the previous procedure above (2.1 g, 3.68 mmol,overall 12.6 g, 22.1 mmol). The tightly sealed reactors are removed fromthe dry box and placed in a heater block with the temperature set at125° C. The reactor tubes are heated overnight (˜16 h). The cooled tubesare taken into the dry box and the contents of the reactor tubes arecombined in a 500 mL round bottom flask. The flask is placed undervacuum to remove the dimethylamine and toluene. The light yellow/greensolid which is left is rinsed with ˜125 mL of cold pentane and filtered,yielding 13.6 g of a light yellow powder for a yield of 65%.

Catalyst H: The reaction is performed inside of a dry box. A 500 mL jaris charged with 250 mL of pentane and the hafnium amide isolated in theprocedure outlined immediately above (13.6 g, 15.5 mmol). The mixture iscooled to −40° C. To the stirring mixture is slowly added 70 mL of a 2.0M trimethyl aluminum (140 mmol) in hexane solution. After 3 h thereaction becomes yellow with a fine, powder precipitating from themixture. The mixture is then cooled to −40° C. and filtered. Theinitially collected product is rinsed with 2×60 mL of cold pentane.10.24 g Catalyst H is isolated (84% yield) with a purity of >99% by ¹HNMR.

Synthesis of Armeenium Borate[methylbis(hydrogenatedtallowalkyl)ammonium tetrakis (pentafluorophenyl) borate]

Armeenium borate can be prepared from ARMEEN® M2HT (available fromAkzo-Nobel), HCl, and Li [B(C₆F₅)₄] according to Example 2 of U.S. Pat.No. 5,919,983.

General 1 Gallon Continuous Solution Propylene/Ethylene I.Copolymerization Procedure

Purified toluene solvent, ethylene, hydrogen, and propylene are suppliedto a 1 gallon reactor equipped with a jacket for temperature control andan internal thermocouple. The solvent feed to the reactor is measured bya mass-flow controller. A variable speed diaphragm pump controls thesolvent flow rate and increases the solvent pressure to the reactor. Thepropylene feed is measured by a mass flow meter and the flow iscontrolled by a variable speed diaphragm pump. At the discharge of thepump, a side stream is taken to provide flush flows for the catalystinjection line and the reactor agitator. The remaining solvent iscombined with ethylene and hydrogen and delivered to the reactor. Theethylene stream is measured with a mass flow meter and controlled with aResearch Control valve. A mass flow controller is used to deliverhydrogen into the ethylene stream at the outlet of the ethylene controlvalve. The temperature of the solvent/monomer is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters, and are combined with the catalystflush solvent. This stream enters the bottom of the reactor, but in adifferent port than the monomer stream. The reactor is run liquid-fullat 500 psig with vigorous stirring. The process flow is in from thebottom and out of the top. All exit lines from the reactor are steamtraced and insulated. Polymerization is stopped with the addition of asmall amount of water, and other additives and stabilizers can be addedat this point. The stream flows through a static mixer and a heatexchanger in order to heat the solvent/polymer mixture. The solvent andunreacted monomers are removed at reduced pressure, and the product isrecovered by extrusion using a devolatilizing extruder. The extrudedstrand is cooled under water and chopped into pellets. The operation ofthe reactor is controlled with a process control computer.

EXAMPLE 1 Propylene/Ethylene Polymerization Using Metallocene Catalyst E(Comparative)

The general procedure for the 1 gallon continuous solutionpolymerization outlined above was employed. A catalyst solutioncontaining 2.6 ppm Zr from Catalyst E was prepared and added to a 4 Lcatalyst storage tank. This solution was combined in a continuous streamwith a continuous stream of a solution containing Armeeniumtetrakis(pentafluorophenyl)borate in toluene and a continuous stream ofa solution of PMAO-IP in toluene to give a ratio of total Ti:B:Al of1:1.2:30. The activated catalyst solution was fed continuously into thereactor at a rate sufficient to maintain the reactor temperature atapproximately 80 degrees C. and a polymer production rate ofapproximately 3 pounds an hour. The polymer solution was continuouslyremoved from the reactor exit and was contacted with a solutioncontaining 100 ppm of water for each part of the polymer solution, andpolymer stabilizers (i.e., 1000 ppm Irgaphos 168 and 1000 ppm Irganox1010 per part of the polymer). The resulting exit stream was mixed,heated in a heat exchanger, and the mixture was introduced into aseparator where the molten polymer was separated from the solvent andunreacted monomers. The resulting molten polymer was extruded andchopped into pellets after being cooled in a water bath. For thisexample, the propylene to ethylene ratio was 22.0. Product samples werecollected over 1 hour time periods, after which time the melt flow ratewas determined for each sample. FIG. 9 is a ¹³C NMR of ComparativeExample 1, and it demonstrates the absence of regio-error peaks in theregion around 15 ppm.

EXAMPLES 2-6

Examples 2-6 were conducted similar to Example 1 except as otherwisenoted in Tables 2-6-1 and 2-6-2 below. Catalyst E is listed forcomparative purposes. FIG. 8 is the ¹³C NMR spectrum of thepropylene/ethylene copolymer product of Example 2. FIGS. 2A and 2B showa comparison of the DSC heating traces of the propylene/ethylenecopolymers of Comparative Example 1 and Example 2.

TABLE 2-6-1 Polymerization Conditions POLY LBS/ Reactor SOLV C2 C3 H2 HRTEMP FLOW FLOW FLOW FLOW production Example DEGC LB/HR LB/HR LB/HR SCCMrate 1 (compar- 80.5 36.0 0.50 11.00 0 3.13 ative) 2 80.5 33.0 0.20 6.0020.8 3.47 3 80.1 26.0 0.10 6.00 14.1 3.09 4 79.9 26.0 0.20 6.00 20.13.25 5 80.0 26.0 0.30 6.00 26.1 3.16 6 80.3 26.0 0.40 6.00 32.1 3.32

TABLE 2-6-2 Monomer conversion and activity catalyst efficiency C3/C2propylene ethylene concentration g metal Example Catalyst ratioconversion conversion ppm(metal) per g polymer 1 (comparative) E 22.0025.7% 64.8% 2.6 6,145,944 2 G 30.17 53.1% 99.1% 25.6 235,823 3 H 61.0748.7% 98.4% 55.0 225,666 4 H 30.34 49.7% 99.0% 55.0 259,545 5 H 20.1746.8% 98.6% 55.0 259,282 6 H 15.00 48.0% 98.7% 55.0 278,579

TABLE 2-6-3 Summary of Polymer Analysis Data DSC MFR Density Cryst. (%)Tg Tc, o Tc, p Example (g/10 min) (kg/dm3) from density (° C.) (° C.) (°C.) 1 72 0.8809 37.9 −26.1 52.3 47.6 2 1.7 0.8740 29.6 −24.8 59.0 49.3 32.2 0.8850 42.8 −10.0 76.6 64.5 4 2.3 0.8741 29.7 −23.2 50.8 41.6 5 20.8648 18.3 −27.1 30.4 10.9 6 2.0 0.8581 9.9 −29.6 — —

TABLE 2-6-4 Summary of Polymer Analysis Data cont'd ΔHc Cryst. (%) Tm, pTm, e ΔHf Cryst. (%) Example (J/g) (from Hc) (° C.) (° C.) (J/g) (fromHf) 1 40.8 24.7 91.9 114.3 52.1 31.6 2 27.1 16.4 64.5 128.9 38.0 23.0 345.0 27.3 102.2 145.7 65.3 39.6 4 30.6 18.5 67.4 145.6 42.9 26.0 5 8.75.3 50.0 119.4 13.0 7.9 6 — — — — — —

TABLE 2-6-5 Summary of Polymer Analysis Data cont'd Ethylene EthyleneRegio-errors Mn Mw Example (wt %)* (mol %)* 14-16 ppm(mol %)* (kg/mol)(kg/mol) MWD 1 9.5 13.6 0.00 58.5 117.4 2.0 2 8.2 11.8 0.24 132.6 315.72.4 3 5.6 8.2 0.46 146.0 318.3 2.2 4 8.2 11.8 0.34 138.5 305.7 2.2 511.1 15.8 0.35 6 13.2 18.6 0.37 127.5 306.8 2.4 *determined by NMR

TABLE 2-6-6 Summary of Polmer Analysis Data cont'd Example % mm* % mr* %rr* 1 98.55 0 1.45 2 98.23 1.09 5.68 3 94.3 2.21 3.43 4 96.37 0 3.63 595.3 0.0 4.66 6 95.17 0 4.83 *corrected PPE + EPE

EXAMPLE 7-8 Homopolymerization of Propylene using Catalyst B and C

Examples 7-8 were conducted similar to Example 1 without ethylene. Theprocedure was similar to Example 1 with exceptions noted in Tables 7-8-1and 7-8-2 below. FIG. 6 shows the ¹³C NMR spectrum of the propylenehomopolymer product of Example 7 prepared using catalyst G. FIG. 7 showsthe ¹³C NMR spectrum of the propylene homopolymer product of Example 8prepared using catalyst H. Both spectra show a high degree ofisotacticity, and the expanded Y-axis scale of FIG. 7 relative to FIG. 6shows more clearly the regio-error peaks. FIGS. 11A-B show the DSCheating and cooling traces of the propylene homopolymer of Example 8.

TABLE 7-8-1 Reactor Conditions and Catalyst Activity Reactor SOLV C3 H2POLY catalyst efficiency TEMP FLOW FLOW FLOW LBS/HR propyleneconcentration g metal Example DEGC LB/HR LB/HR SCCM WEIGHED Catalystconversion ppm(metal) per g polymer 7 99.8 33.1 6.00 1.9 2.30 G 38.3%25.6 111,607 8 100.3 26.0 6.00 2.6 2.57 H 42.8% 32.5 100,987

TABLE 7-8-2 Polymer Analysis DSC MFR Density Cryst. (%) Tg Tc, o Tc, pMn Mw Example (g/10 min) (kg/dm3) from density (° C.) (° C.) (° C.)(kg/mol) (kg/mol) MWD 7 1.9 0.8995 59.7 −6.0 104.2 100.4 114.6 350.8 2.78 2.5 0.9021 62.7 −8.1 105.7 103.3 125.5 334.0 2.7

TABLE 7-8-3 Polymer Analaysis Continued ΔHc Cryst. (%) Tm, p Tm, e ΔHfCryst. (%) Regio-errors Example (J/g) (from Hc) (° C.) (° C.) (J/g)(from Hf) 14-16 ppm(mol %)* % mm** % mr** % rr** 7 76.9 46.6 139.7 153.593.7 56.8 2.69 92.12 5.79 2.08 8 83.6 50.7 144.5 158.2 100.6 61.0 2.3693.93 4.45 1.62 *determined by NMR **corrected PPE + EPE

EXAMPLE 9

This example demonstrates the calculation of B values for certain of theExamples disclosed herein. The polymer from Comparative Example 1 isanalyzed as follows. The data was collected using a Varian UNITY Plus400 MHz NMR spectrometer, corresponding to a ¹³C resonance frequency of100.4 MHz. Acquisition parameters were selected to ensure quantitative¹³C data acquisition in the presence of the relaxation agent. The datawas acquired using gated ¹H decoupling, 4000 transients per data file, a7 sec pulse repetition delay, spectral width of 24,200 Hz and a filesize of 32K data points, with the probe head heated to 130° C. Thesample was prepared by adding approximately 3 mL of a 50/50 mixture oftetrachloroethane-d2/orthodichlorobenzene that is 0.025M in chromiumacetylacetonate (relaxation agent) to 0.4 g sample in a 10 mm NMR tube.The headspace of the tube was purged of oxygen by displacement with purenitrogen. The sample was dissolved and homogenized by heating the tubeand its contents to 150° C., with periodic refluxing initiated by heatgun.

Following data collection, the chemical shifts were internallyreferenced to the mmmm pentad at 21.90 ppm.

For propylene/ethylene copolymers, the following procedure is used tocalculate the percent ethylene in the polymer. Integral regions aredetermined as follows:

TABLE 9-1 Integral Regions for Calculating % Ethylene Region designationppm Integral area A 44-49 259.7 B 36-39 73.8 C 32.8-34   7.72 P31.0-30.8 64.78 Q Peak at 30.4 4.58 R Peak at 30 4.4 F 28.0-29.7 233.1 G  26-28.3 15.25 H 24-26 27.99 I 19-23 303.1Region D is calculated as follows: D=P×(G×Q)/2.Region E is calculated as follows: E=R+Q+(G×Q)/2.

The triads are calculated as follows:

TABLE 9-2 Traid Calculation PPP = (F + A − 0.5D)/2 PPE = D EPE = C EEE =(E − 0.5G)/2 PEE = G PEP = H Moles P = (B + 2A)/2 Moles E = (E + G +0.5B + H)/2For this example, the mole % ethylene is calculated to be 13.6 mole %.For this example, the triad mole fractions are calculated to be asfollows:

TABLE 9-3 Triad Mole Calculation PPP = 0.6706 PPE = 0.1722 EPE = 0.0224EEE = 0.0097 PEE = 0.0442 EPE = 0.0811

From this, the B value is calculated to be (0.172+0.022+0.044+0.081)/2(0.136×0.864)=1.36

In a similar manner, the B values for the following examples arecalculated to be:

TABLE 9-4 B-Value Calculation Example B Value Comparative 1 1.36 2 1.683 1.7 4 1.78 6 1.7

EXAMPLE 10

Table 10 is a summary showing the skewness index, S_(ix), for inventiveand prior art samples. All of the samples were prepared and measured asdescribed in Table C in the Description of the Preferred Embodiments andentitled Parameters Used for TREF. The copolymers of the invention havea skewness index greater than about (−1.2). The results from Table 10are represented graphically in FIG. 12.

The inventive examples show unusual and unexpected results when examinedby TREF. The distributions tend to cover a large elution temperaturerange while at the same time giving a prominent, narrow peak. Inaddition, over a wide range of ethylene incorporation, the peaktemperature, T_(Max), is near 60° C. to 65° C. In the prior art, forsimilar levels of ethylene incorporation, this peak moves to higherelution temperatures with lower ethylene incorporation.

For conventional metallocene catalysts the approximate relationship ofthe mole fraction of propylene, X_(p), to the TREF elution temperaturefor the peak maximum, T_(Max), is given by the following equation:Log_(e) (X _(p))=−289/(273+T _(max))+0.74

For the inventive copolymers, the natural log of the mole fraction ofpropylene, LnP, is greater than that of the conventional metallocenes,as shown in the is equation:LnP>−289/(273+T _(max))+0.75

TABLE 10 Summary of Skewness Index Results Ethylene Elution TemperatureCatalyst Content of Peak maximum Sample No. Type (Mole %) (° C.)Inventive S_(ix) 10-1  Catalyst H 8.2 61.4 0.935 10-2  Catalyst J 8.960.8 −0.697 10-3  Catalyst J 8.5 61.4 −0.642 10-4  Catalyst J 7.6 65.00.830 10-5  Catalyst J 7.6 65.0 0.972 10-6  Catalyst J 8.6 61.4 0.80410-7  Catalyst J 9.6 60.2 −0.620 10-8  Catalyst J 12.4 60.2 0.921 10-9 Catalyst J 8.6 60.8 −0.434 10-10 Catalyst J 8.6 62.0 1.148 10-11Catalyst H — 57.8 1.452 10-12 Catalyst J — 78.2 1.006 10-13 Catalyst H4.4 80.0 −1.021 10-14 Catalyst E 7.6 80.6 −1.388 10-15 Catalyst E 10.070.4 −1.278 10-16 Catalyst E 10.7 66.2 −1.318 10-17 Catalyst F 11.1 69.2−1.296 10-18 Catalyst E 10.6 65.6 −1.266

EXAMPLE 11

DSC analysis shows that propylene/ethylene copolymers produced by asolution polymerization process using a nonmetallocene, metal-centered,pyridal-amine ligand catalyst have melting behavior that differs insurprising ways from propylene/ethylene copolymers produced bymetallocene polymerization processes that are known in the art. Thedifferent melting behavior of these copolymers compared to that ofcopolymers that are known in the art not only demonstrates the noveltyof these materials, but also can be used to infer certain advantages ofthese materials for some applications. The novel aspects of the meltingbehavior of these copolymers and their associated utility are discussedbelow, after first describing the DSC analysis method.

Any volatile materials (e.g., solvent or monomer) are removed from thepolymer prior to DSC analysis. A small amount of polymer, typically fiveto fifteen milligrams, is accurately weighed into an aluminum DSC panwith lid. Either hermetic or standard type pans are suitable. The pancontaining the sample is then placed on one side of the DSC cell, withan empty pan with lid placed on the reference side of the DSC cell. TheDSC cell is then closed, with a slow purge of nitrogen gas through thecell during the test. Then the sample is subjected to a programmedtemperature sequence that typically has both isothermal segments andsegments where the temperature is programmed to increase or decrease ata constant rate. Results that are presented here were all obtained usingheat-flux type DSC instruments manufactured by TA Instruments (e.g.,Model 2910 DSC). The measurement principles underlying heat-flux DSC aredescribed on page 16 of Turi, ibid. The primary signals generated bysuch instruments are temperature (units: ° C.) and differential heatflow (units: watts) into or out of the sample (i.e., relative to thereference) as a function of elapsed time. Melting is endothermic andinvolves excess heat flow into the sample relative to the reference,whereas crystallization is exothermic and involves excess heat flow outof the sample. These instruments are calibrated using indium and othernarrow-melting standards. Calibration ensures that the temperature scaleis correct and for the proper correction of unavoidable heat losses.

Temperature programs for DSC analysis of semi-crystalline polymersinvolve several steps. Although the temperature programs used togenerate the data presented here differed in some details, the criticalsteps were maintained constant throughout. The first step is an initialheating to a temperature sufficient to completely melt the sample; forpolypropylene homopolymers and copolymers, this is 210° C. or higher.This first step also helps insure excellent thermal contact of thepolymer sample with the pan. Although details of this first stepdiffered for data presented here—for example, the rate of heating, theupper temperature, and the hold time at the upper temperature—in allcases the choices were sufficient to achieve the principal objectives ofthis step, of bringing all samples to a common completely meltedstarting point with good thermal contact. The second step involvescooling at a constant rate of 10° C./min from an upper temperature of atleast 210° C. to a lower temperature of 0° C. or less. The lowertemperature is chosen to be at or slightly below the glass transitiontemperature of the particular propylene polymer. The rate ofcrystallization becomes very slow at the glass transition temperature;hence, additional cooling will have little effect on the extent ofcrystallization. This second step serves to provide a standardcrystallization condition, prior to examining subsequent meltingbehavior. After a brief hold at this lower temperature limit, typicallyone to three minutes, the third step is commenced. The third stepinvolves heating the sample from a temperature of 0° C. or lower (i.e.,the final temperature of the previous step) to 210° C. or higher at aconstant rate of 10° C./min. This third step serves to provide astandard melting condition, as preceded by a standard crystallizationcondition. All the melting behavior results presented here were obtainedfrom this third step, that is, from the second melting of the sample.

The output data from DSC consists of time (sec), temperature (° C.), andheat flow (watts). Subsequent steps in the analysis of meltingendotherms are as follows. First, the heat flow is divided by the samplemass to give specific heat flow (units: W/g). Second, a baseline isconstructed and subtracted from the specific heat flow to givebaseline-subtracted heat flow. For the analyses presented here, astraight-line baseline is used. The lower temperature limit for thebaseline is chosen as a point on the high temperature side of the glasstransition. The upper temperature limit for the baseline is chosen as atemperature about 5-10° C. above the completion of the meltingendotherm. Although a straight-line baseline is theoretically not exact,it offers greater ease and consistency of analysis, and the errorintroduced is relatively minor for samples with specific heats ofmelting of about 15-20 Joules per gram or higher. Employing astraight-line baseline in lieu of a more theoretically correct baselinedoes not substantively affect any of the results or conclusionspresented below, although the fine details of the results would beexpected to change with a different prescription of the instrumentalbaseline.

There are a number of quantities that can be extracted from DSC meltingdata. Quantities that are particularly useful in demonstratingdifferences or similarities among different polymers are: (1) the peakmelting temperature, T_(max) (° C.), which is the temperature at whichthe baseline-subtracted heat flow is a maximum (here the convention isthat heat flow into the sample is positive); (2) the specific heat ofmelting, Δh_(m) (J/g), which is the area under the melting endothermobtained by integrating the baseline-subtracted heat flow (dq/dt) (W/g)versus time between the baseline limits; (3) the specific heat flow(dq/dt)_(max) (W/g) at the peak melting temperature; (4) the peakspecific heat flow normalized by the specific heat of melting,{(dq/dt)_(max)/Δh_(m)} (sec⁻¹); (5) the first moment T₁ of the meltingendotherm, defined and calculated as described below; (6) the varianceV₁ (° C²) of the melting endotherm relative to the first moment T₁,defined and calculated as described below; and (7) the square root ofthe variance, V₁ ^(1/2) (° C.), which is one measure of the breadth ofthe melting endotherm.

Treatment of the melting endotherm as a distribution is a useful way toquantify its breadth. The quantity that is distributed as a function oftemperature is the baseline-subtracted heat flow (dq/dt). That this isalso a distribution of temperature is made explicit using the calculuschain rule, (dq/dt)=(dq/dT)(dT/dt) where (dT/dt) is the heating rate.The standard definition of the first moment T₁ of this distribution isgiven by the following equation, where the integrations are carried outbetween the baseline limits. All integrations are most reliablyperformed as (dq/dt) versus time, as opposed to the alternative (dq/dT)versus temperature. In the following equation, (dq/dt) and T are thespecific heat flow and temperature at time t.

$T_{1} = \frac{\int{{T \cdot \left( {{\mathbb{d}q}/{\mathbb{d}t}} \right)}{\mathbb{d}t}}}{\int{\left( {{\mathbb{d}q}/{\mathbb{d}t}} \right){\mathbb{d}t}}}$The variance V₁ relative to the first moment is then standardly definedas:

$V_{1} = \frac{\int{{\left( {T - T_{1}} \right)^{2} \cdot \left( {{\mathbb{d}q}/{\mathbb{d}t}} \right)}{\mathbb{d}t}}}{\int{\left( {{\mathbb{d}q}/{\mathbb{d}t}} \right){\mathbb{d}t}}}$Both V₁ and V₁ ^(1/2) are measures of the breadth of the meltingendotherm.

Results of DSC analyses of both inventive and comparative polymers areshown in Table 11-1. All the samples are propylene/ethylene copolymers,with the exception of Samples 1-4 and 17 which are homopolymers.Polymers 1-16 were made using Catalyst H in a solution process. Polymers17-27 were made with Catalyst E in a solution process. An idea of theprecision of the experimental method plus the data analysis procedure isprovided by replicates (polymers 17, 20, and 22) and by the consistencyof results for sets of polymers that were synthesized under nearlyidentical conditions (polymers 1-4, 7-9, 10-12, and 13-16).

Differences in melting behavior are most easily seen with the aid offigures. FIG. 13 compares the melting endotherms of Samples 8 and 22a.These two propylene/ethylene copolymers have nearly equivalent heats ofmelting and mole percent ethylene contents, about 71 J/g and 8 mole %.However, despite these similarities, the melting behavior of theinventive copolymer (Sample 8) is surprisingly different than that ofthe comparative copolymer (Sample 22a). The melting endotherm of Sample8 is shifted towards lower temperatures and significantly broadened,when comparing at equivalent heat of melting. These changes in meltingbehavior are unique to and characteristic of the copolymers of thisinvention.

Comparison at equivalent heats of melting is particularly meaningful andrelevant. This is because equivalent heats of melting impliesapproximately equal levels of crystallinity, which in turn implies thatthe room temperature moduli should be similar. Therefore, at a givenmodulus or stiffness, the copolymers of this invention possess usefullybroadened melting ranges compared to typical non-inventive copolymers.

FIGS. 14-18, which are derived from the results in Table 11-1, furtherhighlight the differences in melting behavior for the copolymers of thisinvention compared to typical copolymers. For all five of these figures,quantities are plotted as functions of the heat of melting, which asdescribed above is an especially meaningful and relevant basis formaking intercomparisons and inferring utility. For these plots, datahave broken into two series based on the catalyst type used to make thepolymer, either metallocene or nonmetallocene type.

FIG. 14 demonstrates how the peak melting temperature is shifted towardslower temperature for the copolymers of this invention. All the changesin melting behavior, of which this shift in peak melting temperature isbut one example, imply that there are differences in the crystallinestructure at the level of crystal lamellae or other type of primarycrystalline elements. In turn, such differences in crystalline structurecan most reasonably be attributed to differences in microstructure, forexample, the different type of mis-insertion errors or the higher Bvalues that characterize the polymers of this invention. Regardless ofthe exact nature of the microstructural features that give rise to thechanges in melting behavior, the changes are in and of themselvesevidence that the copolymers of this invention are novel compositions.

FIG. 15 which shows a plot of the temperature T_(1%c) at which there isapproximately 1% residual crystallinity, demonstrates another surprisingaspect of the melting behavior of the copolymers of this invention. Thefactor that is used to convert specific heat of melting into nominalweight % crystallinity is 165 J/g=100 weight % crystallinity. (Use of adifferent conversion factor could change details of the results but notsubstantive conclusions.) With this conversion factor, the totalcrystallinity of a sample (units: weight % crystallinity) is calculatedas 100% times Δh_(m) divided by 165 J/g. And, with this conversionfactor, 1% residual crystallinity corresponds to 1.65 J/g. Therefore,T_(1%c) is defined as the upper limit for partial integration of themelting endotherm such that Δh_(m) minus the partial integral equals1.65 J/g, where the same lower limit and baseline are used for thispartial integration as for the complete integration. Surprisingly, forcopolymers catalyzed with a nonmetallocene, metal-centered heteroarylligand catalyst, as compared to metallocene-catalyzed copolymers, this1% residual crystallinity temperature shifts downward less rapidly withincrease in ethylene level (i.e., with decrease in the heat of melting).This behavior of T_(1%c) is similar to that of the final temperature ofmelting T_(me).

FIG. 16, which shows the variance relative to the first moment of themelting endotherm as a function of the heat of melting, demonstratesdirectly the greater breadth of the melting endotherm for the copolymersof this invention.

FIG. 17, which shows the maximum heat flow normalized by the heat ofmelting as a function of the heat of melting, further demonstrates thebroadening of the melting endotherm. This is because, at equivalent heatof melting, a lower peak value implies that the distribution must bebroadened to give the same area. Roughly approximating the shape ofthese melting curves as a triangle, for which the area is given by theformula one-half times the base times the height, then b1/b2=h2/h1. Theinventive copolymers show as much as a four-fold decrease in height,implying a significant increase in breadth.

FIG. 18 illustrates a useful aspect of the broader melting range of theinventive polymers, namely that the rate at which the last portion ofcrystallinity disappears (units: weight % crystallinity per ° C.) issignificantly lower than for metallocene polymers.

The data in Table 11-2 demonstrate in practical terms the utility ofthis broadening of the melting endotherm. Entries in Table 11-2illustrate: (1) the extent to which a greater fraction of melting occursat lower temperatures, which is important for heat seal and bondingapplications, and which is greater for the inventive copolymers; and (2)the extent to which crystallinity remains at higher temperatures and therate at which the final portion of crystallinity disappears, which canbe important for fabrication operations such as thermoforming, foaming,blow molding, and the like, both of which are greater for the inventivecopolymers.

TABLE 11-1 Melting Results from DSC Ethylene Δh_(m) T_(max) T₁(dq/dt)_(max)/Δh_(m) V₁ T_(1%c) Sample* (mole %) (J/g) (° C.) (° C.)(sec⁻¹) (° C.²) (° C.) R_(f) (**) 11-1-1 0.0 90.4 139.0 123.5 0.0109 416143.0 1.60 11-1-2 0.0 94.3 138.8 122.2 0.0105 505 143.1 1.54 11-1-3 0.094.0 139.4 122.4 0.0105 505 143.3 1.60 11-1-4 0.0 95.9 139.5 121.40.0102 576 143.4 1.60 11-1-5 1.5 92.4 138.2 118.4 0.0105 630 142.0 1.4811-1-6 4.3 85.0 120.7 99.2 0.0045 716 135.0 0.40 11-1-7 8.2 67.5 85.983.8 0.0023 909 139.7 0.19 11-1-8 8.2 71.2 93.0 84.4 0.0025 835 137.50.19 11-1-9 8.2 74.6 108.2 87.0 0.0029 790 134.6 0.23 11-1-10 11.8 51.671.7 69.3 0.0024 790 124.4 0.14 11-1-11 11.8 52.5 74.8 69.4 0.0025 781123.7 0.14 11-1-12 11.8 51.9 73.9 69.4 0.0025 802 124.3 0.14 11-1-1315.8 24.0 55.2 66.7 0.0031 667 112.0 0.10 11-1-14 15.8 28.7 55.2 66.30.0026 795 118.0 0.10 11-1-15 15.8 27.6 55.6 66.0 0.0026 783 116.4 0.1011-1-16 15.8 26.9 55.2 66.4 0.0026 769 115.7 0.10 11-1-17a 0.0 120.7160.3 145.3 0.0104 457 165.9 1.43 11-1-17b 0.0 123.9 159.8 144.5 0.0105486 165.2 1.54 11-1-18 . . . 90.3 140.6 125.0 0.0076 419 146.1 1.2111-1-19 . . . 91.3 139.0 123.9 0.0068 374 145.5 1.05 11-1-20a 4.2 110.2137.7 121.8 0.0094 337 144.3 0.95 11-1-20b 4.2 96.5 137.9 121.1 0.0100451 142.7 1.38 11-1-21 . . . 94.6 136.7 120.3 0.0086 385 140.5 1.4311-1-22a 8.0 71.4 117.5 105.8 0.0081 197 124.8 0.74 11-1-22b 8.0 69.7117.0 103.4 0.0080 271 122.8 1.00 11-1-23 . . . 70.1 110.3 91.0 0.0062512 115.9 0.95 11-1-24 . . . 55.9 97.0 78.7 0.0052 436 103.9 0.6711-1-25 . . . 19.8 63.0 61.1 0.0044 188 80.1 0.25 11-1-26 . . . 18.256.6 58.8 0.0049 158 75.3 0.27 *Samples 11-1-1 to −4 made with catalystG, samples −5 to −16 with catalyst H, and −17 to −24 with catalyst E.**Units for R_(f): weight % crystallinity per ° C.

TABLE 11-2 Broadening of the Melting Endotherm Starting FractionFraction Fraction Fraction Crystallinity Melted Melted RemainingRremaining Sample (weight %) at T₁ − 30° C. at T₁ − 20° C. at T₁ + 20°C. at T₁ + 30° C. 11-2-8 43.2 0.153 0.229 0.249 0.134 (inventive)11-2-22a 43.3 0.040 0.112 0.019 0.004 (comparative) 11-2-11 31.8 0.1430.235 0.221 0.131 (inventive) 11-2-25 33.9 0.103 0.170 0.127 0.009(comparative)

EXAMPLE 12

The materials and procedures used to generate the data in Tables 12-1and 12-2 are described below. The data in Tables 12-1 and 12-2 aregraphically presented in FIGS. 19A-B, respectively.

Base Resins:

-   -   Resin I is a Propylene-Ethylene resin prepared via Catalyst H in        solution containing 8 mol % E and with an MFR of 4.7 g/10 min    -   Resin II is a Propylene-Ethylene resin prepared via Catalyst H        in solution containing 16 mol % E and with an MFR of 2.2 g/10        min        Nucleating Agents:    -   A Profax 6823: a polypropylene homopolymer manufactured by        Basell and having a MFR of 0.5 g/10 min.    -   B Experimental resin: a Polypropylene homopolymer with MFR=50        g/10 min    -   C Valtec HH442H: a Polypropylene homopolymer with MFR=1100 g/10        min, Trademark of Basell. Additive C was melt fluxed for 5        minutes at 210C prior to being compounded with base resins.    -   D Profax PF814: a high melt strength polypropylene homopolymer        manufactured by Basell and having a MFR of 3.3 g/10 min    -   E Experimental resin: a Polypropylene homopolymer with MFR=12        g/10 min, reacted with 1000 ppm of        4,4′-oxydibenzenesulfonylazide    -   F Experimental resin: a High Crystallinity Polypropylene        homopolymer with MFR=20 g/10 min.    -   G HDPE DOW Resin 4452N: a High Density Polyethylene with        Density=0.95 kg/dm3 and MI=4 g/10 min    -   H Profax SR256M: a Ziegler-Natta catalyst based        Propylene-Ethylene copolymer containing 3 wt % ethylene, with an        MFR of 2 g/10 min, Tademark of Basell    -   I Millad 3988: a bis-(3,4-dimethylbenzilydine)-sorbitol        clarifier, Trademark of Milliken Chemical    -   J NA 11: methylene-bis-(4,6-di-tert-butylphenyl) phosphate        sodium salt, Trademark of Asahi Denka    -   K Al pTBBA: aluminum bis(p-t-butyl benzoate)hydroxy, from        Dainippon Ink and Chemicals    -   L Hostaperm Red E3B: a quinacridone pigment, Trademark of        Clariant International        Method of Preparation:    -   The base resins and nucleating additives were blended in either        a 50 cc Haake Rheomix 600 or a 20 cc modified Haake Rheomix 600        for 5 minutes at a temperature of 210C at a temperature of 210°        C.

TABLE 12-1 Resin I INCREASE IN ONSET AND PEAK OF CRYSTALLIZATIONTEMPERATURE AFTER ADDITION OF NUCLEATING ADDITIVES FOR RESIN I Increasein Tc after nucleation Nucleating Nucleated resin Delta Tc, Delta Tc,additive Tc, peak Tc, onset peak onset Number Type Conc. (° C.) (° C.)(° C.) (° C.) 12-1-1 None 0.0 68.9 73.1 0.0 0.0 12-1-2 A 1.0 70.4 75.51.5 2.4 12-1-3 A 3.0 75.7 83.9 6.8 10.8 12-1-4 A 10.0 91.7 97.3 22.824.2 12-1-5 B 1.0 72.1 80.2 3.3 7.1 12-1-6 B 3.0 81.0 88.5 12.2 15.412-1-7 B 10.0 95.2 101.1 26.3 28.0 12-1-8 C 1.0 71.3 78.7 2.4 5.6 12-1-9D 1.0 85.3 96.5 16.4 23.4 12-1-10 D 3.0 94.1 105.2 25.2 32.1 12-1-11 D10.0 110.5 127.2 41.6 54.1 12-1-12 E 10.0 112.2 125.0 43.3 51.9 12-1-13F 10.0 98.3 115.7 29.4 42.6 12-1-14 G 10.0 85.0 95.8 16.1 22.7 12-1-15 H10.0 78.2 84.4 9.4 11.3 12-1-16 I 0.2 72.1 113.3 3.2 40.2 12-1-17 J 0.183.3 96.0 14.4 22.9 12-1-18 K 0.2 87.4 101.3 18.5 28.2 12-1-19 L 0.283.8 96.5 14.9 23.4

TABLE 12-2 INCREASE IN ONSET AND PEAK OF CRYSTALLIZATION TEMPERATUREAFTER ADDITION OF NUCLEATING ADDITIVES FOR RESIN II Increase in Tc afterNucleated resin nucleation Nucleating additive Tc, Tc, Delta Tc, DeltaTc, Sample Conc. peak onset peak onset Number Type (wt %) (° C.) (° C.)(° C.) (° C.) 12-2-1 none 0.0 13.5 33.5 0.0 0.0 12-2-2 A 1.0 33.6 51.320.0 17.8 12-2-3 A 3.0 39.9 52.4 26.3 18.9 12-2-4 A 10.0 72.7 89.3 59.255.8 12-2-5 B 1.0 30.5 56.8 16.9 23.3 12-2-6 B 3.0 73.5 84.8 60.0 51.312-2-7 B 10.0 94.8 104.7 81.3 71.2 12-2-8 D 1.0 40.4 97.0 26.8 63.512-2-9 D 3.0 78.7 105.5 65.2 72.0 12-2-10 D 10.0 109.5 129.8 96.0 96.312-2-11 E 10.0 110.5 125.0 97.0 91.5 12-2-12 F 10.0 96.9 80.2 83.4 46.712-2-13 G 10.0 82.2 84.9 68.7 51.4 12-2-14 H 10.0 67.6 71.8 54.1 38.312-2-15 I 0.2 11.8 52.6 0.0 19.1 12-2-16 J 0.1 12.0 35.0 0.0 1.5 12-2-17K 0.2 16.6 37.4 3.1 3.9 12-2-18 L 0.2 17.2 37.4 3.6 3.9

For all of the propylene/ethylene resins tested, the coupled or branchedpolypropylene homopolymer additives D and E show the best nucleation asmeasured by the increase in Tc, peak and by the increase in Tc, onsetafter incorporation of the additive. The nucleation by coupled orbranched polymeric additives is much better than the nucleation by thetypical inorganic nucleators or organic clarifiers typically used inpolypropylene. Propylene homopolymer also shows good nucleation(increase in Tc, peak and Tc, onset), but not as much as the coupled orbranched polypropylenes. Surprisingly, the 50 MFR resin (B) nucleatesbetter than the 0.5 MFR resin (A). Also surprising is that the 1100 MFRresin (C) nucleates even better that the 50 MFR resin (B). The artsuggests to the contrary; that nucleation efficiency increases as MFRdecreases.

Of further interest is that with respect to Resin II, the branched orcoupled polymeric nucleating agents not only shift the onset and peaktemperatures for crystallization, but that they also shift the majorityof base resin crystallization to such markedly higher temperatures thanwhere the unnucleated base resin crystallization occurs. This isespecially surprising for copolymers with higher ethylene content andthus lower crystallinity.

EXAMPLE 13

The materials used to generate the data in Table 13 are described below.The procedure used to blend the base resin with the nucleating agent wasthe same as that used in Example 12. The data in Table 13 is graphicallypresented in FIG. 20.

Base Resins:

-   -   Resin 13-1 is a Propylene-Ethylene resin prepared using Catalyst        H in solution containing 5 mol % (B) and with an MFR of 25 g/10        min.    -   Resin 13-2 is a Propylene-Ethylene resin prepared using Catalyst        H in solution containing 6.7 mol % (B) and with an MFR of 2 g/10        min.    -   Resin 13-3 is a Propylene-Ethylene resin prepared using Catalyst        H in solution containing 12.3 mol % (B) and with an MFR of 2        g/10 min.    -   Resin 13-4 is a Propylene-Ethylene resin prepared using Catalyst        H in solution containing 15.9 mol % (B) and with an MFR of 1.3        g/10 min.    -   Resin 13-5 is a Propylene-Ethylene resin prepared using Catalyst        H in solution containing 8.2 mol % (B) and with an MFR of 4.7        g/10 min    -   Resin 13-6 is a Propylene-Ethylene resin prepared using Catalyst        H in solution containing 15.8 mol % (B) and with an MFR of 2.2        g/10 min    -   Resin 13-7 is a Propylene-Ethylene resin prepared using a        metallocene catalyst in solution, and it contains 13.6 mol % (B)        and with an MFR of 75 g/10 min    -   Resin 13-8 is a Propylene-Ethylene resin prepared using a        metallocene catalyst in solution, and it contains 10.6 mol % (B)        and with an MFR of 26 g/10 min        Nucleating Agent:

-   A Profax PF814: a high melt strength polypropylene homopolymer    manufactured by Basell with an MFR=3.3 g/10 min.    Method of Preparation:    -   The base resin and the nucleating agent were blended in a 50 g        Haake bowl at a temperature of 210C. The weight ratio blend of        base resin to nucleating agent was 97/3 for all samples.

TABLE 13 Tc, Blend Tc, Blend (C) − Tc, Sample No. E (mol %) Tc, Base (C)(C) Base (C) r 13-1 5 81.4 104 22.6 13-2 6.7 71.1 96.1 25 13-3 12.3 47.691 43.4 2.2 13-4 15.9 14.3 88.2 73.9 13-5 8.2 68.9 94.1 25.2 13-6 15.813.5 78.7 64.9 13-7 13.6 50.3 71.7 21.4 1 13-8 10.6 67.7 87.4 19.7 1

Although there is no direct match of ethylene level for any of the baseP/E*resins with any of the base P/E resins, a plot of the differencebetween the Tc, blend temperature and the Tc, base temperature as afunction of ethylene level would clearly show the much greater increasein Tc for the nucleated P/E* resins as compared to nucleated P/E resinsover the entire range of ethylene level. Taking a point by point ratioof the continuous curves represented by the discrete Tc differencevalues of Example 13 for nucleated P/E* and P/E resins indicates that rfor nucleated P/E* is about 1.4 at 5 mole % ethylene and is about 3 at16 mole % ethylene. Furthermore, nucleated P/E* polymer 13-3 exhibits anr value of about 2.2, using as divisor for the Tc difference ofcorresponding P/E resin a value interpolated between that of thenucleated P/E polymers 13-7 and 13-8. P/E* resins demonstrate a muchenhanced crystalline nucleation irrespective of the ethyleneconcentration of the P/E* and comparable P/E.

Although the invention has been described in considerable detail, thisdetail is for the purpose of illustration. Many variations andmodifications can be made on the invention as described above withoutdeparting from the spirit and scope of the invention as described in theappended claims. All publications identified above, specificallyincluding all U.S. patents and allowed U.S. patent applications, areincorporated in their entirety herein by reference.

1. A method of nucleating a propylene homopolymer characterized ashaving ¹³C NMR peaks corresponding to a regio-error at about 14.6 andabout 15.7 ppm, the peaks of about equal intensity, the methodcomprising contacting the propylene homopolymer with an amount of acrystalline or semi-crystalline branched or coupled polymeric nucleatingagent such that the nucleated homopolymer has an r value of at leastabout
 1. 2. The method of claim 1 in which the propylene homopolymer isfurther characterized as having substantially isotactic propylenesequences.
 3. The method of claim 2 in which the nucleating agent is apolyolefin, and the nucleating agent is present in an amount of at leastabout 0.5 weight percent based upon the weight of the propylenehomopolymer.
 4. A method of claim 3 in which the polyolefin is propylenehomopolymer or a copolymer comprising ethylene and propylene.
 5. Anarticle comprising a nucleated homopolymer made by the method of claim1.